BENZIMIDAZOLO[1,2-A]BENZIMIDAZOLE DERIVATIVES FOR ORGANIC LIGHT EMITTING DIODES
Compounds of formula (I) and their use in electronic devices, especially electroluminescent devices: (I) wherein at least two of the substituents R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, or R7 and R8 form together one of the following ring systems (IIa), (IIb) (IIc). When used as charge transport material, charge blocker material and/or host material in electroluminescent devices, the compounds of formula (I) may provide improved efficiency, stability, manufacturability, or spectral characteristics of electroluminescent devices and reduced driving voltage of electroluminescent devices.
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The present invention relates to compounds of formula (I) and their use in electronic devices, especially electroluminescent devices. When used as charge transport material, charge blocker material and/or host material in electroluminescent devices, the compounds of formula (I) may provide improved efficiency, stability, manufacturability, or spectral characteristics of electroluminescent devices and reduced driving voltage of electroluminescent devices.
Khan, Misbahul Ain; Ribeiro, Vera Lucia Teixeira, Pakistan Journal of Scientific and Industrial Research 43 (2000) 168-170 describes the synthesis of benzimidazo[1,2-a]benzimadozoles
(R═H, Me, Et) by trialkyl phosphite-induced deoxygenation and thermolysis of 1-(o-nitrophenyl)- and 1-(o-azidophenyl)benzimidazoles.
Pedro Molina et al. Tetrahedron (1994) 10029-10036 reports that aza Wittig-type reaction of bis(iminophosphoranes), derived from bis(2-aminophenyl)amine with two equivalents of isocyanate directly provided benzimidazo[1,2,a]benzimidazole derivatives.
R=iso-propyl and R′=ethyl)
Kolesnikova, I. V.; Zhurnal Organicheskoi Khimii 25 (1989) 1689-95 describes the synthesis of 5H-benzimidazo[1,2-a]benzimidazole 1,2,3,4,7,8,9,10-octafluoro-5-(2,3,4,5,6-pentafluorophenyl).
Achour, Reddouane; Zniber, Rachid, Bulletin des Societes Chimiques Belges 96 (1987) 787-92 describes the synthesis of benzimidazobenzimidazoles
(R═H, —CH(CH3)2) which were prepared from benzimidazolinone derivatives.
Hubert, Andre J.; Reimlinger, Hans, Chemische Berichte 103 (1970) 2828-35 describes the synthesis of benzimidazobenzimidazoles
X. Wang et al. Org. Lett. 2012, 14, 452-455 discloses a highly efficient copper-catalyzed synthesis for compounds of formula
wherein compounds of formula
are reacted in the presence of copper acetate (Cu(OAc)2)/PPh3/1,10-phenathroline/sodium acetate and oxygen in m-xylene (1 atm) at elevated temperature. Among others the following compounds can be prepared by the described synthesis method:
In Eur. J. Org. Chem. 2014, 5986-5997 a new synthesis of benzimidazolo[1,2-a]benzimidazole is described.
In RSC Advances 2014, 4, 21904-21908 a new synthesis of benzimidazolo[1,2-a]benzimidazole is described.
It is mentioned—as a general statement—that these polycyclic molecules have—besides other applications—also attracted great interest in the field of electroluminescent devices.
WO2011/160757 relates to an electronic device comprising an anode, cathode and at least one organic layer which contains a compound of formulae
wherein X may be a single bond and L may be a divalent group. The following 4H-Imidazo[1,2-a]imidazole compounds are explicitly disclosed:
WO2012/130709 relates to 4H-Imidazo[1,2-a]imidazoles
such as, for example,
a process for their production and their use in electronic devices, especially electroluminescent devices.
WO2014/009317 relates to compounds of formula
especially compounds of formula
such as, for example,
a process for their production and their use in electronic devices, especially electroluminescent devices. The 2,5-disubstituted benzimidazo[1,2-a]benzimidazole derivatives are suitable hole transporting materials, or host materials for phosphorescent emitters.
Notwithstanding these developments, there remains a need for organic light emitting devices comprising new materials, especially host (=matrix) materials, charge transport materials, especially hole transport materials, and/or charge blocker materials, especially electron/exciton blocker materials, to provide long lifetimes, improved efficiency, stability, manufacturability, driving voltage and/or spectral characteristics of electroluminescent devices.
Accordingly, it is an object of the present invention, with respect to the aforementioned relevant art, to provide further materials suitable for use in OLEDs and further applications in organic electronics. More particularly, it should be possible to provide charge transport materials, especially hole transport materials, charge blocker materials, especially electron/exciton blocker materials and host (=matrix) materials for use in OLEDs. The materials should be suitable especially for OLEDs which comprise at least one emitter, which is preferably a phosphorescence emitter, for example at least one green, red or yellow emitter, especially at least one green emitter or at least one red emitter.
Furthermore, the materials should be suitable for providing OLEDs which ensure good efficiencies, good operative lifetimes and a high stability to thermal stress, and a low use and operating voltage of the OLEDs.
Said object is solved by a compound of formula (I)
wherein
at least two of the substituents R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, or R7 and R8 form together one of the following ring systems
preferably a ring system of formula IIa or IIb, more preferably a ring system of formula IIb;
X is NR19, O, S, C(R28)2, or Si(R28)2;
R9 and R19 are independently of each other group of formula -(A1)o-(A2)p-(A3)q-(A4)r-R20; preferably, R9 and R19 are identical; in a further preferred embodiment, especially in the case that at least two of the substituents R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, or R7 and R8 together form a ring system (IIc), R9 and R19 are different;
R1, R2, R3, R4, R5, R6, R7, R8, which are not forming together a ring system of formula IIa, IIb or IIc are independently of each other H or group of formula -(A1′)o′-(A2′)p′-(A3′)q′-(A4′)r′-R20′ or a group E; or adjacent groups R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, and/or R7 and R8 can from together a ring;
R10, R11, R12, R13 are independently of each other H, CN or group of formula -(A1′)o′-(A2′)p′-(A3′)q′-(A4′)r′-R20′ or a group E; or
adjacent groups R10 and R11, R11 and R12 and/or R12 and R13 can from together a ring;
o is 0, or 1, p is 0, or 1, q is 0, or 1, r is 0, or 1, preferably o is 0, or 1, p is 0, or 1, q is 0 and r is 0;
o′ is 0, or 1, p′ is 0, or 1, q′ is 0, or 1, r′ is 0, or 1,
A1, A2, A3, A4 are independently of each other a C6-C24 arylene group which is unsubstituted or substituted by G, C2-C24 heteroarylene group which is unsubstituted or substituted by G; R20 is a C6-C30 aryl group which is unsubstituted or substituted by G, C2-C60 heteroaryl group which is unsubstituted or substituted by G, a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D; or, in the case that at last one of o, p, q and r is 1, R20 is CN; A1′, A2′, A3′, A4′ are independently of each other a C6-C24 arylene group which is unsubstituted or substituted by G, C2-C24 heteroarylene group which is unsubstituted or substituted by G;
R20′ is H, CN, a C6-C30 aryl group which is unsubstituted or substituted by G, C2-C60 heteroaryl group which is unsubstituted or substituted by G, a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D;
R28 is independently of each other C6-C18aryl which is unsubstituted or substituted by C1-C18alkyl or C1-C18alkoxy; or C1-C18alkyl which is interrupted by —O—, which is unsubstituted or substituted by E; or two residues R28 can together with the carbon atom or Si atom to which they are bonded form a ring;
D is —CO—, —COO—, —S—, —SO—, —SO2—, —O—, —CR63═CR64—, —NR65—, —SiR70R71—, —POR72—, or —C≡C—, preferably —O—, —NR65—, —SiR70R71—;
E is —OR69, —SR69, —NR65R66, —COR68, —COOR67, —CONR65R66, —CN, —Si(R70)3 or halogen, preferably —NR65R66, —CN, —Si(R70)3
G is E, or a C1-C24alkyl group, a C6-C24aryl group, a C6-C24aryl group, which is substituted by F, C1-C24alkyl, C1-C24alkyl which is interrupted by O, a C2-C30heteroaryl group, or a C2-C30heteroaryl group, which is substituted by F, C1-C24alkyl, C1-C24alkyl which is interrupted by O; preferably E;
R63 and R64 are independently of each other C6-C18aryl; C6-C18aryl which is substituted by C1-C18alkyl or C1-C18alkoxy; C1-C18alkyl; or C1-C18alkyl which is interrupted by —O—;
R65 and R66 are independently of each other a C6-C18aryl group; a C6-C18aryl which is substituted by C1-C18alkyl or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—; or
R65 and R66 together form a five or six membered ring,
R67 is a C6-C18aryl group; a C6-C18aryl group, which is substituted by C1-C18alkyl, or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—;
R68 is H; a C6-C18aryl group; a C6-C18aryl group, which is substituted by C1-C18alkyl or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—;
R69 is a C6-C18aryl; a C6-C18aryl, which is substituted by C1-C18alkyl or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—;
R70 and R71 are independently of each other a C1-C18alkyl group, a C6-C18aryl group, or a C6-C18aryl group, which is substituted by C1-C18alkyl; and
R72 is a C1-C18alkyl group, a C6-C18aryl group, or a C6-C18aryl group, which is substituted by C1-C18alkyl.
The combination of the benzimidazo[1,2-a]benzimidazole structure with a ring system of formula (IIa), (IIb) or (IIc) gives rise to materials that are highly suitable in devices that emit green, red or yellow light, preferably green or red light, more preferably green light. Devices are achieved resulting in low voltages and high external quantum efficiencies (EQE's) and/or long lifetimes.
The compounds of the present invention may be used for electrophotographic photoreceptors, photoelectric converters, organic solar cells (organic photovoltaics), switching elements, such as organic transistors, for example, organic FETs and organic TFTs, organic light emitting field effect transistors (OLEFETs), image sensors, dye lasers and electroluminescent devices, such as, for example, organic light-emitting diodes (OLEDs).
Accordingly, a further subject of the present invention is directed to an electronic device, comprising a compound according to the present invention. The electronic device is preferably an electroluminescent device, such as an organic light-emitting diode (OLED).
The compounds of formula (I) can in principal be used in any layer of an EL device, but are preferably used as host, charge transport (i.e. hole transport or electron transport) material, especially hole transport and/or charge/exciton blocking (i.e. hole/exciton blocking or electron exciton blocking) material, especially electron/exciton blocking material. Particularly, the compounds of formula (I) are used as host material for green, red and yellow, preferably green and red, more preferably green light emitting, preferably phosphorescent, emitters.
Hence, a further subject of the present invention is directed to a charge transport layer, especially a hole transport layer, comprising a compound of formula (I) according to the present invention.
A further subject of the present invention is directed to an emitting layer, comprising a compound of formula (I) according to the present invention. In said embodiment a compound of formula (I) is preferably used as host material or as co-host material together with one or more, preferably one, further host materials. More preferably, a combination of a compound of formula (I) and optionally a co-host material together with a phosphorescent emitter is used.
A further subject of the present invention is directed to a charge/exciton blocking layer, especially an electron/exciton blocking layer, comprising a compound of formula (I) according to the present invention.
The terms halogen, alkyl, alkoxy, cycloalkyl, aryl, aryloxy, aralkyl, heteroaryl, arylene, heteroarylene generally have the following meaning, if said groups are not further specified in specific embodiments mentioned below:
Halogen is fluorine, chlorine, bromine and iodine, preferably fluorine.
C1-C25alkyl, preferably C1-C24alkyl and more preferably C1-C18alkyl are typically linear or branched, where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, or octadecyl. C1-C8alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl. C1-C4alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl.
The alkyl groups mentioned above can optionally be substituted by E and/or interrupted by D. Preferably, the alkyl groups mentioned above are unsubstituted or can optionally be substituted by E.
C1-C25alkoxy groups and preferably C1-C18alkoxy groups are straight-chain or branched alkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, un-decyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octade-cyloxy. Examples of C1-C8alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1,1,3,3-tetramethylbutoxy and 2-ethylhexyloxy, preferably C1-C4alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy.
The term “cycloalkyl group” is preferably C5-C12cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted by G.
C6-C30aryl, preferably C6-C24aryl and more preferably C6-C18aryl, which is unsubstituted or optionally can be substituted by G, is most preferably phenyl, 4-methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl, or 2-naphthyl, biphenylyl, triphenylyl, fluoranthenyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, or anthryl, which may be unsubstituted or substituted by G. Phenyl, 1-naphthyl and 2-naphthyl are examples of a C6-C10aryl group.
C2-C60heteroaryl, preferably C2-C30heteroaryl, more preferably C2-C24 heteroaryl, most preferably C2-C18 heteroaryl, further most preferably C2-C13 heteroaryl represents a ring with five, six or seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible heteroatoms, and is typically a heterocyclic group with five to 60 atoms, preferably with five to 30 atoms, more preferably with five to 24 atoms, most preferably with five to 18 atoms, further most preferably with five to 13 atoms having at least six conjugated t-electrons such as thienyl, benzothiophenyl, dibenzothiophenyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, iso-benzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quin-olizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, 4-imidazo[1,2-a]benzimidazoyl, 5-benzimidazo[1,2-a]benzimidazoyl, benzimidazolo[2,1-b][1,3]benzothiazolyl, carbazolyl, azatriphenylyl, azadibenzofuryl, azadibenzothiophenyl, azacarbazolyl, quinolonyl, isoquinolinyl, quinoxalinyl, quinazolinyl, phenanthrolinyl, phenanthridinyl, benzo[h]quinolonyl, benz[h]isoquinolinyl, benzo[f]isoquinolinyl, benzo[f]quinolinyl, benzo[h]quinazolinyl, benzo[f]quinazolinyl, dibenzo[f,h]quinolonyl, dibenzo[f,h]isoquinolonyl, dibenzo[f,h]quinoxalinyl, dibenzo[f,h]quinazolinyl or phenoxazinyl, which can be unsubstituted or substituted by G. Benzimidazo[1,2-a]benzimidazo-5-yl, benzimidazo[1,2-a]benzimidazo-2-yl, carbazolyl and dibenzofuranyl are examples of a C2-C14heteroaryl group.
The group C2-C60heteroaryl, preferably C2-C30heteroaryl, more preferably C2-C24heteroaryl, most preferably C2-C18heteroaryl, further most preferably C2-C13 heteroaryl, may be unsubstituted or substituted by G.
A C2-C3heteroaryl group is for example, in addition to the groups mentioned above, benzimidazo[1,2-a]benzimidazo-5-yl
benzimidazo[1,2-a]benzimidazo-2-yl
benzimidazolo[2,1-b][1,3]benzothiazolyl, benzimidazolo[2,1-b][1,3]benzoxazole, carbazolyl, dibenzofuranyl, or dibenzotihophenyl, which can be unsubstituted or substituted by G, especially by C6-C10aryl, or C6-C10aryl, which is substituted by C1-C4alkyl; or C2-C13heteroaryl.
C2-C60heteroaryl, preferably C2-C30heteroaryl, more preferably C2-C24heteroaryl, most preferably C2-C18 heteroaryl, further most preferably C2-C13 heteroaryl means that the heteroaryl residue comprises at least 2 carbon atoms and at most 60 carbon atoms in the base skeleton (without substituents). The further atoms in the heteroaryl base skeleton are heteroatoms (N, O and/or S).
R24′ is in each case independently C1-C18alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-C14aryl, such as phenyl, tolyl, naphthyl, phenanthronyl, triphenylenyl, fluoranthenyl or biphenylyl.
C1-C24heterocyclic group, preferably C1-C13heterocyclic group, more preferably C2-C13 heterocyclic group represents a ring with five, six or seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible heteroatoms, and is typically a heterocyclic group with five to 24 atoms, preferably with five to 13 atoms. The heterocyclic group may be a C1-C24heteroaryl group as defined above or a C1-C24heterocycloalkyl group which may be unsubstituted or substituted by G. Typical C1-C24heterocycloalkyl groups are oxetan, tetrahydrofuran, tetrahydropyran, oxepane, dioxane, azetidine, pyrrolidine, piperidine, hexahydroazepine, hexahydrodiazepin, tetrahydrothiophene, thietan, tetrahydrothiopyran, thiepan, morpholine as well as bridged heterocycloalkyl systems such as oxabicy-clo[4.4.0]decane and azabicyclo[2,2,1]undecane.
C6-C24arylene groups, preferably C6-C10arylene groups, which optionally can be substituted by G, preferably C6-C10arylene groups, which optionally can be substituted by G, are more preferably phenylene, 4-methylphenylene, 4-methoxyphenylene, naphthylene, especially 1-naphthylene, or 2-naphthylene, biphenylylene, triphenylylene, fluoranthenylene, terphenylylene, pyrenylene, 2- or 9-fluorenylene, phenanthrylene, or anthrylene, which may be unsubstituted or substituted by G. Preferred C6-C24arylen groups, preferably C6-C10arylene groups are 1,3-phenylene, 3,3′-biphenylylene, 3,3′-m-terphenylene, 2- or 9-fluorenylene, phenanthrylene, which may be unsubstituted or substituted by G.
C2-C30heteroarylene groups, preferably C2-C14heteroarylene groups, which are unsubstituted or optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible heteroatoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated-electrons such as thienylene, benzothiophenylene, dibenzothiophenylene, thianthrenylene, furylene, furfu-rylene, 2H-pyranylene, benzofuranylene, isobenzofuranylene, dibenzofuranylene, phenoxy-thienylene, pyrrolylene, imidazolylene, pyrazolylene, pyridylene, bipyridylene, triazinylene, pyrimidinylene, pyrazinylene, pyridazinylene, indolizinylene, isoindolylene, indolylene, indazolylene, purinylene, quinolizinylene, chinolylene, isochinolylene, phthalazinylene, naphthyridinylene, quinoxalinylene, quinazolinylene, cinnolinylene, pteridinylene, carbolinylene, benzotriazolylene, benzoxazolylene, phenanthridinylene, acridinylene, pyrimidinylene, phenanthrolinylene, phenazinylene, isothiazolylene, phenothiazinylene, isoxazolylene, furazanylene, carbazolylene, benzimidazo[1,2-a]benzimidazo-2,5-ylene, or phenoxazinylene, which can be unsubstituted or substituted by G. Preferred C2-C30heteroarylen groups are pyridylene, triazinylene, pyrimidinylene, carbazolylene, dibenzofuranylene, azatriphenylylene, azadibenzofurylene, aza-dibenzothiophenylene, azacarbazolylene, quinolonylene, isoquinolinylene, quinoxalinylene, quinazolinylene, phenanthrolinylene, phenanthridinylene, benzo[h]quinolonylene, benz[h]isoquinolinylene, benzo[f]isoquinolinylene, benzo[f]quinolinylene, benzo[h]quinazolinylene, benzo[f]quinazolinylene, dibenzo[f,h]quinolonylene, dibenzo[f,h]isoquinolonylene, dibenzo[f,h]quinoxalinylene, dibenzo[f,h]quinazolinylene and benzimidazo[1,2-a]benzimidazo-2,5-ylene
which can be unsubstituted or substituted by G, preferably substituted by C6-C10aryl, C6-C10aryl which is substituted by C1-C4alkyl; or C2-C13heteroaryl.
If a substituent occurs more than one time in a group, it can be different in each occurrence.
The wording “substituted by G” means that one, or more, especially one, two or three substituents G might be present. Preferred substituents G are mentioned below.
The wording “substituted by E” means that one, or more, especially one, two or three substituents E might be present. Preferred substituents E are mentioned below.
As described above, the aforementioned alkyl groups may be substituted by E and/or, if de-sired, interrupted by D. Interruptions are of course possible only in the case of groups containing at least 2 carbon atoms connected to one another by single bonds; C6-C18aryl is not interrupted; interrupted arylalkyl contains the unit D in the alkyl moiety. C1-C18alkyl substituted by one or more E and/or interrupted by one or more units D is, for example, (CH2CH2O)1-9—Rx, where Rx is H or C1-C10alkyl or C2-C10alkanoyl (e.g. CO—CH(C2H5)C4H9), CH2—CH(ORy′)—CH2—O—Ry, where Ry is C1-C18alkyl, C5-C12cycloalkyl, phenyl, C7-C15phenylalkyl, and Ry′ embraces the same definitions as Ry or is H.
Halo-C1-C8alkyl is an alkyl group (as defined above) where at least one of the hydrogen atoms is replaced by a halogen atom. Examples are —CF3, —CF2CF3, —CF2CF2CF3, —CF(CF3)2, —(CF2)3CF3, and —C(CF3)3.
This means, that an alkyl group substituted by E is, for example, an alkyl group where at least one of the hydrogen atoms is replaced by F. Examples are —CF3, —CF2CF3, —CF2CF2CF3, —CF(CF3)2, —(CF2)3CF3, and —C(CF3)3.
D is —CO—, —COO—, —S—, —SO—, —SO2—, —O—, —NR65—, —SiR70R71—, —POR72—, —CR63═CR64— or —C≡C. Suitable residues R63, R64, R65, R70 R71 and R72 are mentioned above. D is preferably —CO—, —COO—, —S—, —SO—, —SO2—, —O—, —NR65—, wherein R65 is preferably C1-C18alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or C6-C14aryl, such as phenyl, tolyl, naphthyl, triphenylyl or biphenylyl, or C_C30heteroaryl, such as, for example, benzimidazo[1,2-a]benzimidazo-2-yl
carbazolyl, dibenzofuranyl, which can be unsubstituted or substituted especially by C6-C10aryl, or C6-C10aryl, which is substituted by C1-C4alkyl; or C2-C13heteroaryl.
R24′ is C1-C18alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-C14aryl, such as phenyl, tolyl, naphthyl, phenanthronyl, triphenylenyl, fluoranthenyl or biphenylyl.
E is —OR69, —SR69, —NR65R66, —COR68, —COOR67, —CONR65R66, —CN, —Si(R70)3 or halogen. E is preferably —OR69; —SR69; —NR65R66; —COR68; —COOR67; —CON65R66; F or —CN; wherein R65, R66, R67, R68 and R69 are preferably independently of each other C1-C18alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-C14aryl, such as phenyl, tolyl, naphthyl, triphenylyl or biphenylyl.
G is E, or a C1-C24alkyl group, an unsubstituted C6-C30aryl group or a C6-C30aryl group, which is substituted by G, whereby G is preferably F, C1-C24alkyl, or C1-C24alkyl which is interrupted by O; an unsubstituted C2-C60heteroaryl group or a C2-C60heteroaryl group, which is substituted by G, whereby G is preferably F, C1-C18alkyl, or C1-C18alkyl which is interrupted by O. G is preferably—OR69, —SR69, —NR65R66; a C1-C18alkyl group, an unsubstituted C6-C18aryl group, a C6-C18aryl group, which is substituted by F, or C1-C18alkyl; an unsubstituted C2-C24heteroaryl group, or a C2-C24heteroaryl group, which is substituted by F, or C1-C18alkyl; wherein R65, R66 and R69 are independently of each other C1-C18alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-C14aryl, such as phenyl, tolyl, naphthyl, or biphenylyl. More preferably, G is a C6-C18aryl group like phenyl, tolyl, triphenylyl or biphenylyl, or a C6-C24heteroaryl group like dibenzothiophenylyl, dibenzofuranyl, pyridyl, triazinyl, pyrimidinyl, azatriphenylyl, azadibenzofuryl, azadibenzothiophenyl, azacarbazolyl, quinolonyl, isoquinolinyl, quinoxalinyl, quinazolinyl, phenanthrolinyl, phenanthridinyl, benzo[h]quinolonyl, benz[h]isoquinolinyl, benzo[f]isoquinolinyl, benzo[f]quinolinyl, benzo[h]quinazolinyl, benzo[f]quinazolinyl, dibenzo[f,h]quinolonyl, dibenzo[f,h]isoquinolonyl, dibenzo[f,h]quinoxalinyl or dibenzo[f,h]quinazolinyl.
Compound of Formula (I)
In the compound of formula (I), at least two of the substituents R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, or R7 and R8, preferably at least two of the substituents R1 and R2, R2 and R3, R3 and R4, or R6 and R7, more preferably R2 and R3 or R6 and R7, form together one of the following ring systems
preferably a ring system of formula IIa or IIb, more preferably a ring system of formula IIb.
In a further embodiment, compounds of formula (I) are preferred, wherein at least two of the substituents R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, or R7 and R8, preferably at least two of the substituents R1 and R2, R2 and R3, R3 and R4, or R6 and R7, more preferably R2 and R3 or R5 and R6 or R6 and R7, form together a ring system of formula (IIc).
The residues R10 to R13 and the group X have been defined before and further preferred residues R10 to R13 and the group X are defined below. Preferably, X is NR19 or C(R28)2.
Preferably, two of the substituents R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, or R7 and R8, more preferably, two of the substituents R1 and R2, R2 and R3, R3 and R4, or R6 and R7, most preferably R2 and R3 or R6 and R7, form together a ring system of formula IIa, IIb or 11c, preferably R2 and R3 form together a ring system of formula IIa or IIb, more preferably a ring system of formula Ib. In a further preferred embodiment, R6 and R7, form together a ring system of formula IIc.
Most preferred compounds of formula (I) are compounds (I-IIa), (I-IIa′), (I-IIb), (I-IIb′), (I-IIc), (I-IIc′), (I′-II′a), (I′-II′a′), (I′-II′b), (I′-II′b′), (I′-II′c) and (I′-II′c′), as well as the compounds (I″-IIc), (I-IIc″), (I″-II″c), (I″-II″c″), (I′″-IIc), (I-IIc′″), (I′″-II′″c) and (I′″-II′″c′″):
The residues R1 to R13 and the group X have been defined before and further preferred residues R1 to R13 and the group X are defined below. Preferably, X is NR19 or C(R28)2.
Of said compounds (I-IIa), (I-IIa′), (I-IIb), (I-IIb′), (I-IIc), (I-IIc′), (I′-II′a), (I′-II′a′), (I′-II′b), (I′-II′b′), (I′-II′c) and (I′-II′c′), the compounds (I-IIb′) and (I-IIb), are especially preferred. Further, the compounds (I-IIc), (I-IIc′), (I′-II′c) and (I′-II′c′) and the compounds (I″-IIc), (I-IIc″), (I″-II″c), (I″-II″c″), (I′″-IIc), (I-Ic′″), (I′″-II′″c) and (I′″-II′″c′″) are especially preferred.
In the compounds of formula (I), X is NR19, O, S, C(R28)2, or Si(R28)2. Preferably, X is NR19, O, S or C(R28)2.
In the case that at least two of the substituents R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, or R7 and R8 form together a ring system of formula (IIa) or (IIb), preferably (IIb), X is more preferably, X is NR19 or C(R28)2 and most preferably, X is NR19.
In the case that at least two of the substituents R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, or R7 and R8 form together a ring system of formula (IIc), X is more preferably NR19, O or C(R28)2. Further more preferably, X is in this case NR19 or C(R28)2.
Therefore, especially preferred compounds are the compounds (I-IIa), (I-IIa′), (I-IIb), (I-IIb′), (I-IIc), (1-IIc′), (I′-II′a), (I′-II′a′), (I′-II′b), (I′-II′b′), (I′-II′c) and (I′-II′c′), wherein X is NR19 or C(R28)2. Most preferably, X is NR19. Further especially preferred compounds are the compounds (I″-IIc), (I-IIc″), (I″-II″c), (I″-II″c″), (I′″-IIc), (I-IIc′″), (I′″-II′″c) and (I′″-II′″c′″) wherein X is NR19 or C(R28)2.
Most preferred compounds—in the case that X is NR19—are compounds I-IIc, I-IIc′″, I′-II′c′ and I″-IIc.
Even more preferred compounds are—in one embodiment—the compounds (I-IIa), (I-IIa′), (I-IIb), (I-IIb′), (I′-II′a), (I′-II′a′), (I′-II′b) or (I′-II′b′), especially preferably compounds (I-IIa), (I-IIa′), (I-IIb) and (I-IIb′), even more preferred (I-IIb) and (I-IIb′), wherein X is NR19.
Even more preferred compounds are—in a further embodiment—the compounds (I-IIc), (I-IIc′), (I′-II′c) and (I′-II′c′), wherein X is C(R28)2.
Also even more preferred compounds are—in a further embodiment—the compounds (I-IIc), (I-IIc′), (I′-II′c) and (I′-II′c′), wherein X is NR19.
Also even more preferred compounds are—in a further embodiment—the compounds (I-IIc″), (I″-II″c), (I′″-IIc) and (I′″-II′″c′″) wherein X is C(R28)2.
Also even further more preferred compounds are—in a further embodiment—the compounds (I″-IIc), (I″-II″c″), (I-Ic′″) and (I′″-II′″c) wherein X is NR19.
The residues R1 to R13, R19 and R28 have been defined before and further preferred residues R1 to R13, R19 and R28 are defined below.
Most preferred are therefore the following compounds:
Further most preferred compounds are:
The residues R1 to R13, R19 and R28 have been defined before and further preferred residues R1 to R13, R19 and R28 are defined below.
From the compounds mentioned above, compounds (I-IIb), (I-IIb′), (I′-II′cb), (I′-II′c′b), (I-IIcb), (I-IIc′b), (I′-II′ca), (I′-II′c′a), (I-IIca), (I-IIc′a), (I-IIc″b), (I″-II″cb), (I′″-IIcb), and (I′″-II′″c′″b), (I″-IIca), (I″-II″c″a), (I-IIc′″a) and (I′″-II′″ca), and (I′″-II′″c′″a) are more preferred.
Compounds (I′-II′c′b), (1-IIc′b), (I′-II′c′a), (1-IIca), (I″-IIca) and (I-IIc′″a) are even more preferred.
Compounds I-IIb and I-IIb′ are even more most preferred.
A1, A2, A3, A4, A1′, A2′, A3′ and A4′
A1, A2, A3, A4, A1′, A2′, A3′ and A4′ are independently of each other a C6-C24 arylene group which is unsubstituted or substituted by G, C2-C24 heteroarylene group which is unsubstituted or substituted by G;
A1, A2, A3, A4, A1′, A2′, A3′ and A4′ are preferably independently of each other C6-C24arylene groups, which optionally can be substituted by G, selected from the group consisting of phenylene, naphthylene, especially 1-naphthylene, or 2-naphthylene, biphenylene, triphenylene, terphenylene, pyrenylene, 2- or 9-fluorenylene, phenanthrylene, or anthrylene, which may be unsubstituted or substituted by G; or
C5-C24heteroarylene groups, and C2-C24heteroarylene groups, which optionally can be substituted by G, characterized by a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible heteroatoms, and having at least six conju-gated-electrons, preferably selected from benzothiophenylene, thianthrenylene, furylene, furfu-rylene, 2H-pyranylene, benzofuranylene, isobenzofuranylene, dibenzofuranylene
dibenzothiophenylene
carbazolylene
imidazolylene, pyrazolylene, pyridylene, bipyridylene, triazinylene, pyrimidinylene, pyrazinylene, pyridazinylene, indolizinylene, isoindolylene, indolylene, indazolylene, purinylene, quinolizinylene, chinolylene, isochinolylene, phthalazinylene, naphthyridinylene, chinoxalinylene, chinazolinylene, cinnolinylene, pteridinylene, carbolinylene, benzotriazolylene, benzoxazolylene, phenanthridinylene, pyrimidinylene, benzimidazo[1,2-a]benzimidazo-2,5-ylene, which can be unsubstituted or substituted by G; R73 is a C6-C24aryl group, or a C2-C30heteroaryl group, which can optionally be substituted by G; wherein the lines are bonding sites;
preferably, A1, A2, A3, A4, A1′, A2′, A3′ and A4′ are
which can be unsubstituted or substituted by G, preferably unsubstituted or substituted by 1, 2, 3 or 4 groups G, more preferably unsubstituted or substituted by 1 or 2 groups G, most preferably unsubstituted; whereby G is defined above and is most preferably —NR65R66, —CN, —Si(R70)3, a C1-C24alkyl group, an unsubstituted C6-C30aryl group or a C2-C30heteroaryl group; R73 is a C6-C18aryl group; a C6-C18aryl which is substituted by C1-C18alkyl or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—, preferably C1-C18alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-C14aryl, such as phenyl, tolyl, naphthyl, or biphenylyl;
R38 a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G, or a C1-C24heteroaryl group, which can optionally be substituted by G; and/or two adjacent groups of the groups may form together with the atom to which they are bonded a ring structure, which can optionally be substituted by G; R130 is independently in each occurrence H or C6-C24arylene group, which can optionally be substituted by G, or a C2-C30heteroarylene group, which can optionally be substituted by G; wherein G is as defined in above; wherein the dotted lines are bonding sites;
wherein (C)— has the meaning that the bonding site of the group A1, A2, A3, A4, A1′, A2′, A3′ and A4′ is linked to a C-atom, and (N)— has the meaning that the bonding site of the group A1, A2, A3, A4, A1′, A2′, A3′ and A4′ is linked to a N-atom, and (C,N) has the meaning that the bonding site of the group A1, A2, A3, A4, A1′, A2′, A3′ and A4′ is linked to a C or N-atom.
A1, A2, A3, A4, A1′, A2′, A3′ and A4′ are more preferably in each occurrence independently of each other a group of the formula:
preferably
preferably
which can be unsubstituted or substituted by G, preferably unsubstituted or substituted by 1, 2, 3 or 4 groups G, more preferably unsubstituted or substituted by 1 or 2 groups G, most preferably unsubstituted; whereby G is defined above and is most preferably —NR65R66, —CN, —Si(R70)3, a C1-C24alkyl group, an unsubstituted C6-C30aryl group or a C2-C30heteroaryl group; R73 is a C6-C18aryl group; a C6-C18aryl which is substituted by C1-C18alkyl or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—, preferably C1-C18alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-C14aryl, such as phenyl, tolyl, naphthyl, or biphenylyl;
wherein (C)— has the meaning that the bonding site of the group A1, A2, A3, A4, A1′, A2′, A3′ and A4′ is linked to a C-atom, and (N)— has the meaning that the bonding site of the group A1, A2, A3, A4, A1′, A2′, A3′ and A4′ is linked to a N-atom, and (C,N) has the meaning that the bonding site of the group A1, A2, A3, A4, A1′, A2′, A3′ and A4′ is linked to a C or N-atom; and the dotted lines are bonding sites.
A1, A2, A3, A4, A1′, A2′, A3′ and A4′ are most preferably in each occurrence independently of each other a group of the formula:
which can be unsubstituted or substituted by G, preferably unsubstituted or substituted by 1, 2, 3 or 4 groups G, more preferably unsubstituted or substituted by 1 or 2 groups G, most preferably unsubstituted; whereby G is defined above and is most preferably NR65R66, —CN, a C1-C24alkyl group, an unsubstituted C6-C30aryl group or a C2-C30heteroaryl group, wherein the dotted lines are bonding sites.
Further most preferably, A1, A2, A3, A4, A1′, A2′, A3′ and A4′ are in each occurrence independently of each other 1,3-phenylene, 1,4-phenylene,
R20 and R20′
R20 is a C6-C30 aryl group which is unsubstituted or substituted by G, C2-C60 heteroaryl group which is unsubstituted or substituted by G, a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D; or, in the case that at last one of o, p, q and r is 1, R20 is CN;
R20′ is H, CN, a C6-C30 aryl group which is unsubstituted or substituted by G, C2-C60 heteroaryl group which is unsubstituted or substituted by G, a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D.
The groups G, E and D are defined above.
Preferably, R20′ is H, CN or has one of the definitions given for R20 mentioned below.
Preferably, R20 is
or, in the case that at last one of o, p, q and r is 1, CN;
wherein
X1 is S, O, C(R21)2, NR23;
R21 is a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G, or a C1-C24heteroaryl group, which can optionally be substituted by G; and/or two adjacent groups of the groups R21 may form together with the atom to which they are bonded a ring structure, which can optionally be substituted by G;
R22 is a C6-C18 aryl group which is unsubstituted or substituted by G, C2-C18 heteroaryl group which is unsubstituted or substituted by G;
R23 is a C6-C18 aryl group which is unsubstituted or substituted by G, C2-C18 heteroaryl group which is unsubstituted or substituted by G;
R24 and R25 are independently of each other H, a C6-C18 aryl group which is unsubstituted or substituted by G, C2-C18 heteroaryl group which is unsubstituted or substituted by G, a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D, or —CN;
a is 0, 1, 2 or 3, preferably 0, 1 or 2;
b is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;
the dotted lines are bonding sites; or
wherein
X1, X2 and X3 are independently of each other CR16 or N, wherein in formula (8) at least one of X1 to X3 is N, and wherein in formulae (9) and (10) at least one of X1 and X3 is N;
Ar1 and Ar2 are independently of each other a C6-C24 aryl group, which is optionally substituted by G, or a C1-C24 heteroaryl group, which is optionally substituted by G;
R16, R17 and R18 are independently of each other H, a C6-C24 aryl group which can be substituted by G, a C1-C24 heteroaryl group which can be substituted by G or a C1-C25alkyl group, which can optionally be substituted by E and/or interrupted by D; preferably, H; or
R26, R27, R28 and R29 are independently of each other H, a C6-C24 aryl group which can be substituted by G, a C1-C24 heteroaryl group which can be substituted by G or a C1-C25alkyl group, which can optionally be substituted by E and/or interrupted by D; or a substituent E; preferably, H or CN, more preferably H;
e is 0, 1, 2, 3, 4 or 5; preferably 0, 1, 2 or 3; more preferably 0, 1 or 2;
f is 0, 1, 2 or 3; preferably 0, 1 or 2; more preferably 0;
g is 0, 1, 2, 3 or 4; preferably 0, 1 or 2; more preferably 0 or 1;
h is 0, 1 or 2, preferably 0 or 1; more preferably 0;
or
two adjacent groups R26, R27 R28 or R29 may form together with the atoms to which they are bonded a ring structure which may be substituted by G,
wherein ˜ is a bonding site.
Preferred groups (2), (3), (4), (5), (6) and (7) are:
wherein X1 is O or S;
wherein ˜ is a bonding site.
Most preferred groups (2), (3), (4), (5), (6) and (7) are:
wherein ˜ is a bonding site.
Preferred groups (8), (9) and (10) are:
wherein
Ar1 and Ar2 are independently of each other a C6-C24 aryl group, which is optionally substituted by G, or a C1-C24 heteroaryl group, which is optionally substituted by G;
˜ are bonding sites to the neighboring groups.
The group G is described above.
Preferably, Ar1 and Ar2 are unsubstituted phenyl or a group of the following formula
wherein
˜ are bonding sites to the neighboring groups.
Most preferably, Ar1 and Ar2 are unsubstituted phenyl.
Most preferably, the groups (8), (9) and (10) are
wherein
the dotted lines are bonding sites to the neighboring groups.
Preferred groups (11), (12), (13), (14) and (15) are
wherein
˜ are bonding sites to the neighboring groups.
Most preferred groups (11), (12), (13), (14) and (15) are:
wherein
˜ are bonding sites to the neighboring groups.
Most preferably, R20′ is H, CN, or has one of the definitions for R20 mentioned below: Most preferably, R20 is
wherein
˜ and the dotted lines are bonding sites to the neighboring groups.
o is 0 or 1, p is 0 or 1, q is 0 or 1, r is 0 or 1; preferably, o is 0 or 1, p is 0 or 1 and q and rare 0, more preferably, o is 0 or 1 and p, q and r are 0.
o′ is 0 or 1, p′ is 0 or 1, q′ is 0 or 1, r′ is 0 or 1; preferably, o′ is 0 or 1, p′ is 0 or 1 and q′ and r′ are 0, more preferably, o′ is 0 or 1 and p′, q′ and r′ are 0.
R9 and R19
R9 and R19 are independently of each other group of formula -(A1)o-(A2)p-(A3)q-(A4)r-R20; preferably, R9 and R19 are identical.
In a further preferred embodiment, especially in the case that at least two of the substituents R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, or R7 and R8 together form a ring system (IIc), R9 and R19 are different.
The groups A1, A2, A3 and A4, the indices o, p, q and r and the residue R20 are defined above and preferred specific combinations of groups A1, A2, A3 and A4, indices o, p, q and r and the residue R20 are defined below.
Preferably, R9 and R19 are independently of each other a -(A1)o-C1-C25alkyl group, which can optionally be substituted by E; a -(A1)o-C6-C24aryl group, which can optionally be substituted by G, or a -(A1)o-C1-C24heteroaryl group, which can optionally be substituted by G, wherein A1 and o are defined above, most preferably A1 is 1,2-phenylene, 1,3-phenylene or 1,4-phenylene and o is 0 or 1;
more preferably, R9 and R19 are independently of each other
wherein
X1 is S, O, C(R21)2, NR23;
R22 is a C6-C18 aryl group which is unsubstituted or substituted by G, C2-C18 heteroaryl group which is unsubstituted or substituted by G;
R23 is H, a C6-C18 aryl group which is unsubstituted or substituted by G, C2-C18 heteroaryl group which is unsubstituted or substituted by G;
R24 and R25 are independently of each other H, a C6-C18 aryl group which is unsubstituted or substituted by G, C2-C18 heteroaryl group which is unsubstituted or substituted by G, a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D, or —CN;
a is 0, 1, 2 or 3, preferably 0, 1 or 2;
b is 0, 1, 2, 3 or 4, preferably 0, 1 or 2; or
wherein
X1, X2 and X3 are independently of each other CR16 or N, wherein in formula (8) at least one of X1 to X3 is N, and wherein in formulae (9) and (10) at least one of X1 and X3 is N;
Ar1 and Ar2 are independently of each other a C6-C24 aryl group, which is optionally substituted by G, or a C1-C24 heteroaryl group, which is optionally substituted by G;
R16, R17 and R18 are independently of each other H, a C6-C24 aryl group which can be substituted by G, a C1-C24 heteroaryl group which can be substituted by G or a C1-C25alkyl group, which can optionally be substituted by E and/or interrupted by D; preferably, H; or
R26, R27, R28 and R29 are independently of each other H, a C6-C24 aryl group which can be sub stituted by G, a C1-C24 heteroaryl group which can be substituted by G or a C1-C25alkyl group, which can optionally be substituted by E and/or interrupted by D; or a substituent E; preferably, H or CN, more preferably H;
e is 0, 1, 2, 3, 4 or 5; preferably 0, 1, 2 or 3; more preferably 0, 1 or 2;
f is 0, 1, 2 or 3; preferably 0, 1 or 2; more preferably 0;
g is 0, 1, 2, 3 or 4; preferably 0, 1 or 2; more preferably 0 or 1;
h is 0, 1 or 2, preferably 0 or 1; more preferably 0;
or
two adjacent groups R26, R27 R28 or R29 may form together with the atoms to which they are bonded a ring structure which may be substituted by G,
wherein the dotted line is a bonding site, wherein the group -(A1)o- is defined above and is preferably phenylene or a single bond, more preferably a single bond. Also more preferably 1,3-phenylene.
The groups G, E and D are defined above.
Preferred groups (2-1) to (15-1) are mentioned above in the definition of R20, whereby the bonding site is replaced by a group -(A1)o-, and preferred groups A1 are also mentioned above. o is 0 or 1.
More preferred groups R9 and R19 are independently of each other:
wherein the dotted lines are bonding sites.
In addition to the groups mentioned above, more preferred groups R9 and R19 are independently of each other
Most preferred groups R9 and R19 are independently of each other:
wherein the dotted lines are bonding sites.
R28R28 is independently of each other C6-C18aryl which is unsubstituted or substituted by C1-C18alkyl or C1-C18alkoxy; or C1-C18alkyl which is interrupted by —O—, which is unsubstituted or substituted by E; or two residues R28 can together with the carbon atom or Si atom to which they are bonded form a ring. Preferably, two residues R28 bonded to the same carbon atom or Si atom are identical.
The group E has been defined above.
In the case that two residues R28 can together with the carbon atom or Si atom to which they are bonded form a ring, said ring is preferably a saturated aliphatic ring, an unsaturated aliphatic ring having one or two double bonds, an unsaturated heteroaliphatic ring having one or two double bonds and comprising one, two or three heteroatoms selected from N, O and S or an aromatic ring. More preferably, said ring comprises 5 to 10 ring atoms, even more preferably 5 to 7 ring atoms.
Preferably, R28 is independently of each other C6-C18aryl which is unsubstituted or substituted by C1-C18alkyl or C1-C18alkoxy; or C1-C18alkyl which is interrupted by —O—, which is unsubstituted or substituted by E.
More preferably, R28 is independently of each C1-C18alkyl, especially methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, or octadecyl, further more preferably C1-C8alkyl, especially methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, and most preferably C1-C4alkyl, especially methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl. Further most preferably, R28 is in each case methyl.
R1, R2, R3, R4, R5, R6, R7, R8, which are not forming together a ring system of formula IIa, IIb or IIc and R10, R11, R12, R13
R1, R2, R3, R4, R5, R6, R7, R8, which are not forming together a ring system of formula IIa, IIb or IIc are independently of each other H, CN or group of formula -(A1′)o′-(A2′)p′-(A3′)q′-(A4′)r′-R20′ or a group E; or adjacent groups R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, and/or R7 and R8 can from together a ring.
R10, R11, R12, R13 are independently of each other H, CN or group of formula -(A′)o′-(A2′)p′-(A3′)q′-(A4′)r′-R20′ or a group E; or
adjacent groups R10 and R11, R11 and R12 and/or R12 and R13 can from together a ring.
The groups A1′, A2′, A3′ and A4′, the indices o′, p′, q′ and r′ and the residue R20′ are defined above.
Preferably, R1, R2, R3, R4, R5, R6, R7 and R8, which are not forming together a ring system of formula IIa, IIb or IIc are independently of each other H, CN, a -(A1′)o′-C6-C18 aryl group which is unsubstituted or substituted G, a -(A1′)o′-C2-C18 heteroaryl group which is unsubstituted or substituted G or a -(A1′)o′-C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D, wherein A1′ and o′ are defined above, preferably A1′ is 1,2-phenylene, 1,3-phenylene or 1,4-phenylene and o′ is 0 or 1.
More preferably, R1, R2, R3, R4, R5, R6, R7 and R8, which are not forming together a ring system of formula IIa, IIb or IIc are independently of each other H, CN, a C6-C18 aryl group which is unsubstituted or substituted G, a C2-C18 heteroaryl group which is unsubstituted or substituted G or a C1-C25alkyl group, which can optionally be substituted by E and/or interrupted by D.
Most preferably, R1, R2, R3, R4, R5, R6, R7 and R8, which are not forming together a ring system of formula IIa, IIb or IIc are independently of each other H, CN or one of R5, R6, R7 and R8 is a C6-C18 aryl group which is unsubstituted or substituted G, a C2-C18 heteroaryl group which is unsubstituted or substituted G or a C1-C25alkyl group, which can optionally be substituted by E and/or interrupted by D, and all other R1, R2, R3, R4, R5, R6, R7 and R8 are H; or
R1, R2, R3, R4, R5, R6, R7 and R8, which are not forming together a ring system of formula IIa, IIb or IIc are independently of each other H, CN or one of R1, R2, R3 and R4 is a C6-C18 aryl group which is unsubstituted or substituted G, a C2-C18 heteroaryl group which is unsubstituted or substituted G or a C1-C25alkyl group, which can optionally be substituted by E and/or interrupted by D, and all other R1, R2, R3, R4, R5, R6, R7 and R8 are H.
Further most preferably, R1, R2, R3, R4, R5, R6, R7, R8, which are not forming together a ring system of formula IIa, IIb or IIc are H.
The groups G, E and D have been defined before.
Preferably, R10, R11, R12 and R13 are independently of each other H, CN, a -(A1′)o′-C6-C18 aryl group which is unsubstituted or substituted G, a -(A1′)o′-C2-C18 heteroaryl group which is unsubstituted or substituted G or a -(A1′)o′-C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D, wherein A1′ and o′ are defined above, preferably A1′ is 1,2-phenylene, 1,3-phenylene or 1,4-phenylene and o′ is 0 or 1
More preferably, R10, R11, R12 and R13 are independently of each other H, CN, a C6-C18 aryl group which is unsubstituted or substituted G, a C2-C18 heteroaryl group which is unsubstituted or substituted G or a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D.
Most preferably, R10, R11, R12 and R13 are independently of each other H, CN or one of R10, R11, R12 and R13 is a C6-C18 aryl group which is unsubstituted or substituted G, a C2-C18 heteroaryl group which is unsubstituted or substituted G or a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D, and all other R10, R11, R12 and R13 are H.
Most preferably, R10, R11, R12 and R13 are H.
The groups G, E and D have been defined before.
Most preferred compounds of formula (I) are therefore the following compounds: (I-IIaH), (I-IIa′H), (I-IIbH), (I-IIb′H), (I-IIcH), (I-IIc′H), (I′-II′aH), (I′-II′a′H), (I′-II′bH), (I′-II′b′H), (I′-II′cH) and (I′-II′c′H):
wherein X is NR19 or C(R28)2, preferably NR19, and R9, R19 and R28 have been defined above.
Further most preferred compounds of formula (I) are the following compounds:
(I″-IIcH), (I-IIc″H), (I″-II″cH), (I″-II″c″H), (I′″-IIcH), (I-IIc′″H), (I′″-II′″cH), and (I′″-II′c′″H):
wherein X is NR19 or (R28)2, and R9, R9 and R28 have been defined above.
Of said compounds (I-IIaH), (I-IIa′H), (I-IIbH), (I-IIb′H), (I-IIcH), (I-IIc′H), (I′-II′aH), (I′-II′a′H), (I′-II′bH), (I′-II′b′H), (I′-II′cH) and (I′-II′c′H), the compounds (I-IIa′H) and (I-IIbH) are especially preferred.
Even more most preferred compounds are—in one embodiment—the compounds (I-IIaH), (I-IIa′H), (I-IIbH), (1-IIb′H), (I′-II′aH), (I′-II′a′H), (I′-II′bH) or (I′-II′b′H), especially preferably compounds (I-IIaH), (I-IIa′H), (I-IIbH) and (I-IIb′H), even more preferred (I-IIbH) and (I-IIb′H), wherein X is NR19.
Further especially preferred compounds are the compounds (I-IIcH), (I′-II′c′H), (I″-IIcH), (I″-II″c″H), (I-IIc″H) and (I′″-II′″cH) in the case that X is NR19.
Further especially preferred compounds are the compounds (I-IIc′H), (I′-II′c′H), (I-IIc″H), (I″-II″cH), (I′″-IIcH) and (I′″-II′″c′″H) in the case that X is C(R28)2.
Even more most preferred compounds are—in a further embodiment—the compounds (I-IIcH), (I-IIc′H), (I′-II′cH) and (I′-II′c′H), wherein X is C(R28)2.
Further even more most preferred compounds are—in a further embodiment—the compounds (I-IIcH), (I-IIc′H), (I′-II′cH), (I-IIc′″H) and (I′-II′c′H), wherein X is NR19.
Also even more preferred compounds are—in a further embodiment—the compounds (I″-IIcH), (I″-II″c″H), (I-IIc′″H) and (I′″-II′″cH) wherein X is NR19.
Also even more preferred compounds are—in a further embodiment—the compounds (I′-II′c′H) and (I-IIc′H) wherein X is C(R28)2.
The residues R9, R19 and R28 have been defined before.
Most preferred are therefore the following compounds:
Further most preferred compounds are:
Further most preferred compounds are:
The residues R9, R19 and R28 have been defined before.
Specific examples of the compounds represented by the formula (I) are given below. The compounds represented by the formula (I) are not limited to the following specific examples.
The dotted lines are bonding sites.
The dotted lines are bonding sites.
The dotted lines are bonding sites.
The dotted lines are bonding sites.
The dotted lines are bonding sites.
The dotted lines are bonding sites.
Very specific examples for compounds of formula (I) are:
Generally, the heterocyclic derivatives of formula (I) are prepared in analogy to the preparation processes described in the art, e.g. in WO2012/130709, WO2014/009317, WO2014/044722, European patent application no. 13191100.0, WO2015/014791, European patent application no. EP14197947.9 and European patent application no. EP14197952.6.
The present invention further relates to a process for the preparation of the heterocyclic derivatives of formula (I) comprising:
- i) Preparation of a compound of formula (I), wherein R6 and R7 form together a ring system of formula IIa, comprising:
- ia) preparation of an intermediate of formula IIIa;
-
- ib) cyclization, whereby a compound of formula (I) is formed;
- ii) Preparation of a compound of formula (I), wherein R2 and R3 form together a ring system of formula IIb, comprising:
- iia) preparation of an intermediate of formula IIIb or IIIb′;
-
- iib) cyclization, whereby a compound of formula (I) is formed;
- iii) Preparation of a compound of formula (I), wherein R2 and R3 form together a ring system of formula IIc, comprising:
- iiia) preparation of an intermediate of formula IIIc;
-
- iiib) cyclization, whereby a compound of formula (IIId) is formed;
-
- iiic) functionalization of the NH group, whereby a compound of formula (I) is formed;
- iv) Preparation of a compound of formula (I), wherein R2 and R3 form together a ring system of formula IIc, comprising:
- iva) preparation of an intermediate of formula IIIe;
-
- ivb) cyclization, whereby a compound of formula (I) is formed;
- v) Preparation of a compound of formula (I), wherein R6 and R7 form together a ring system of formula IIc, comprising:
- va) preparation of an intermediate of formula IIIf;
-
- vb) cyclization, whereby a compound of formula (I) is formed;
- vi) Preparation of a compound of formula (I), wherein R6 and R7 form together a ring system of formula IIIc, comprising:
- via) preparation of an intermediate of formula IIIg;
-
- vib) cyclization, whereby a compound of formula (I) is formed;
- vii) Preparation of a compound of formula (I), wherein R6 and R7 form together a ring system of formula IIc, comprising:
- viia) preparation of an intermediate of formula IIIh;
-
- viib) cyclization, whereby a compound of formula (I) is formed;
- viii) Preparation of a compound of formula (I), wherein R6 and R7 form together a ring system of formula IIc, comprising:
- viiia) preparation of an intermediate of formula IIIi;
wherein Hal is halogen, preferably Br or Cl, more prefera-byl C1;
-
- viiib) cyclization, whereby a compound of formula (IIIj) is formed;
-
- viiic) functionalization of the NH group, whereby a compound of formula (I) is formed;
- ix) Preparation of a compound of formula (I), wherein R2 and R3 form together a ring system of formula IIc, comprising:
- ixa) preparation of an intermediate of formula IIIk;
wherein Hal is halogen, preferably Br or Cl, more preferably Cl;
-
- ixb) cyclization, whereby a compound of formula (IIIl) is formed;
-
- ixc) functionalization of the NH group, whereby a compound of formula (I) is formed;
wherein the residues R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and R13 are described above.
Specific reaction conditions of the steps i) to vii) of the process according to the present invention are described below as well as in the example part of the present application.
- i) Synthesis scheme with reaction conditions for the preparation of a compound of formula (I), wherein R6 and R7 form together a ring system of formula IIa:
- ii) Synthesis schemes with reaction conditions for the preparation of a compound of formula (I), wherein R2 and R3 form together a ring system of formula IIb:
Specific conditions for the reaction steps shown in the schemes above are described for example in the example part and in Organic Letters, 14(6), 1432-1435; 2012, Organic Letters, 4(20), 3481-3484; 2002, Chemical Communications (Cambridge, United Kingdom), 50(85), 12911-12914; 2014, and Journal of Fluorine Chemistry, 40(2-3), 217-46; 1988.
- iii) Synthesis scheme with reaction conditions for the preparation of a compound of formula (I), wherein R2 and R3 form together a ring system of formula IIc:
Specific conditions for the reaction steps shown in the schemes above are described for example in the example part and in Bulletin des Societes Chimiques Belges, 96(10), 787-92; 1987, Org. Lett. 2014, 16, 98-101, Journal of Molecular Catalysis A: Chemical 352 (2012) 110-127, European Polymer Journal 52 (2014) 181-192, WO12130709A1, Synlett, (1), 127-133; 2005, Organic Letters, 17(2), 346-349; 2015, WO2009148016 (K2CO3, NMP), and WO2009148062 (K2CO3, NMP).
- iv) Synthesis scheme with reaction conditions for the preparation of a compound of formula (I), wherein R2 and R3 form together a ring system of formula IIc:
An analogous reaction is for example described in WO2011128017.
- v) Synthesis scheme with reaction conditions for the preparation of a compound of formula (I), wherein R6 and R7 form together a ring system of formula IIc:
An analogous reaction is for example described in WO14009317.
- vi) Synthesis scheme with reaction conditions for the preparation of a compound of formula (I), wherein R6 and R7 form together a ring system of formula IIc:
Analogous reactions are for example described in Org. Lett. 2011, 13, 20, 5504 (ring system); J. Am. Chem. Soc. 2011, 133, 9250-9253, Org. Lett. 2012, 14, 4, 1078 (dibenzofurane).
- vii) Synthesis schemes with reaction conditions for the preparation of a compound of formula (I), wherein R6 and R7 form together a ring system of formula IIc:
Analogous reactions are for example described in Synthetic Communications 1, 42: 497-505, 2012; Chem. Eur. J. 2009, 15, 8275-8282; (CF3COOH, Pyridine/H2O); Chemical Communications (Cambridge, United Kingdom), (13), 1548-1550; 2008; Organic Letters, 16(2), 342-345; 2014; Org. Lett. 2014, 16, 342-345; Organic Letters, 9(10), 1863-1866; 2007; Inorganic Chemistry, 53(23), 12532-12539; 2014; New Journal of Chemistry, 39(8), 6513-6521; 2015; Journal of Organic Chemistry, 73(23), 9207-9213; 2008; WO2010083873; WO2010083872 and WO2010131855.
or
Analogous reactions are for example described for example in New J. Chem. 2015, 39, 6513-6521.
is prepared as follows:
2-iodo-5-phenyl-benzimidazolo[1,2-a]benzimidazole is prepared as describe in WO 2014/009317.
In the following, reaction conditions for the preparation and functionalization of the base skeleton
are given.
- viii) Synthesis scheme with reaction conditions for the preparation of a compound of formula (I), wherein R6 and R7 form together a ring system of formula IIc
and functionalization of the NH group, for example by one of the following two alternatives:
- ix) Synthesis scheme with reaction conditions for the preparation of a compound of formula (I), wherein R2 and R3 form together a ring system of formula IIc
and functionalization of the NH group, for example by one of the following two alternatives:
The compounds of formula (I), wherein two of the substituents R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, or R7 and R8 form together the following ring system
wherein X is NR19, are prepared as shown in the following general reaction schemes:
I) R5 and R6, R6 and R7, or R7 and R8 form together a ring system of formula (Ic)
Reaction Step I-1Suitable reaction conditions for step I-1 are for example: Pd2(dba)3, Xantphos, tBuONa, toluene Suitable reaction conditions for step I-2 are for example: Pd(OAc)2, PCy3*HBF4, K2CO3, DMA
More detailed reaction conditions are mentioned below.
Specific examples for Intermediates I-1, I-2 and I-3 are shown in the following table:
wherein Hal is Cl or Br.
Detailed reaction conditions are mentioned below.
Specific examples for the reaction step I-3, wherein R19-Hal is R19—Cl, are shown in the following table:
Specific examples for the reaction step I-3, wherein R19-Hal is R19—Br, are shown in the following table:
II) R1 and R2, R2 and R3, or R3 and R4 form together a ring system of formula (Ic)
Reaction Step I-1Suitable reaction conditions for step II-1 are for example: Pd2(dba)3, Xantphos, tBuONa, toluene Suitable reaction conditions for step II-2 are for example: Pd(OAc)2, PCy3*HBF4, K2CO3, DMA
More detailed reaction conditions are mentioned below.
Specific examples for Intermediates II-1, II-2 and II-3 are shown in the following table:
wherein Hal is Cl or Br.
Detailed reaction conditions are mentioned below.
Specific examples for the reaction step II-3, wherein R19-Hal is R19—Cl, are shown in the following table:
Specific examples for the reaction step II-3, wherein R19-Hal is R19—Br, are shown in the following table:
Suitable reaction conditions for step I-1 and step I-1:
The molar ratio between the intermediate I-1 respectively II-1 and 2-chloroanolone is usually 2:1 to 1:2.5, preferably 1.5:1 to 1:2, more preferably 1.3:1 to 1:1.5, most preferably 1.1:1 to 1:1.5 and further most preferably 1:1.5.
Suitable catalysts in the reaction step I-1 respectively II-1 mentioned above are preferably selected from the group consisting of Pd2(dba)3 and Pd(OAc)2.
Suitable ligands in the reaction mentioned above are preferably selected from the group consisting of Xantphos, tBu3P*HBF4, tBu3P, (+−)BINAP, BrettPhos, XPhos, PCy3*HBF4, PCy3 preferably Xantphos. An overview of suitable ligands and catalysts are given in Chem.Sci., 2011, 2, 27.
Suitable bases in the reaction step I-1 respectively II-1 mentioned above are preferably selected from the group consisting of potassium phosphate tribasic (K3PO4), K2CO3, Na2CO3, Cs2CO3, NaOtBu and KOtBu, preferably NaOtBu. It is also possible to use a mixture of two or more bases.
The reaction step I-1 respectively II-1 mentioned above is preferably carried out in a solvent. Suitable solvents are for example toluene, xylene, dioxane, THF and tBuOH or mixtures of the solvents mentioned before, preferably toluene and xylene.
The reaction temperature in the reaction step I-1 respectively II-1 mentioned above is usually 20° C. to 220° C., preferably 50° C. to 200° C., more preferably 60° C. to 190° C., most preferably 60° C. to 180° C.
The reaction time in the reaction step I-1 respectively II-1 mentioned above is usually 10 minutes to 72 hours, preferably 30 minutes to 24 hours, more preferably 2 hours to 16 hours.
The reaction pressure is not critical and usually atmospheric pressure.
Suitable Reaction Conditions for Step I-2 and Step II-2:Suitable catalysts in the reaction step I-2 respectively II-2 mentioned above are preferably selected from the group consisting of Pd2(dba)3 and Pd(OAc)2.
Suitable ligands in the reaction step I-2 respectively II-2 mentioned above are preferably selected from the group consisting of PCy3*HBF4, PCy3, Xantphos, tBu3P*HBF4,tBu3P, (+−)BINAP, BrettPhos and XPhos, preferably PCy3*HBF4, PCy3. An overview of suitable ligands and catalysts are given in Chem.Sci., 2011, 2, 27.
Suitable bases in the reaction step I-2 respectively II-2 mentioned above are preferably selected from the group consisting of potassium phosphate tribasic (K3PO4), K2CO3, Na2CO3, Cs2CO3, NaOtBu, KOtBu and DBU, preferably K2CO3. It is also possible to use a mixture of two or more bases.
The reaction mentioned above is preferably carried out in a solvent. Suitable solvents are for example toluene, xylene, dioxane, dimethyl acetamide (DMA), dimethyl formamide (DMF), dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP) and 1,3-dimethyl imidazolidone (DMI), or mixtures thereof, preferably DMA.
The reaction temperature in the reaction step I-2 respectively II-2 mentioned above is usually 20° C. to 220° C., preferably 50° C. to 200° C., more preferably 60° C. to 190° C., most preferably 60° C. to 180° C.
The reaction time in the reaction step I-2 respectively II-2 mentioned above is usually 10 minutes to 72 hours, preferably 30 minutes to 24 hours, more preferably 2 hours to 16 hours.
The reaction pressure is not critical and usually atmospheric pressure.
Suitable Reaction Conditions for Step I-3 and Step II-3, Wherein R19-Hal is R19 Cl:
The molar ratio between the compound of formula I-3 respectively II-3 and R19—CI is usually 2:1 to 1:2.5, preferably 1.5:1 to 1:2, more preferably 1.3:1 to 1:1.5, most preferably 1.1:1 to 1:1.5 and further most preferably 1:1.5.
Suitable bases in the reaction step I-3 respectively II-3 mentioned above are preferably selected from the group consisting of NaH, n-BuLi, t-BuLi and lithium hexamethyldisilazide. It is also possible to use a mixture of two or more bases.
The reaction step I-3 respectively II-3 mentioned above is preferably carried out in a solvent. Suitable solvents are for example THF, dioxane, dimethyl formamide (DMF), or mixtures thereof, preferably THF with n-BuLi as a base or DMF with NaH as a base.
The reaction temperature in the reaction step I-3 respectively II-3 mentioned above is usually −78° C. to 200° C., preferably −78° C. to 150° C., more preferably −78° C. to 120° C., most preferably −78° C. to 100° C.
The reaction time in the reaction step I-3 respectively II-3 mentioned above is usually 10 minutes to 72 hours, preferably 30 minutes to 24 hours, more preferably 2 hours to 16 hours.
The reaction pressure is not critical and usually atmospheric pressure.
Suitable Reaction Conditions for Step I-3 and Step II-3, Wherein R19-Hal is R19 Br:
The molar ratio between the compound of formula I-3 respectively II-3 and R19—Br is usually 2:1 to 1:2.5, preferably 1.5:1 to 1:2, more preferably 1.3:1 to 1:1.5, most preferably 1.1:1 to 1:1.5 and further most preferably 1:1.5.
The reaction step I-3 respectively II-3 mentioned above is preferably carried out in a solvent. Suitable solvents are alcohols, for example tert. butanol, (polar) aprotic solvents, for example tertiary carboxylic acid amides like dimethyl acetamide (DMA), dimethyl formamide (DMF), di-methyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl imidazolidone (DMI), nitrobenzene, or mixtures thereof.
The reaction step I-3 respectively II-3 mentioned above is preferably carried out in the presence of a catalyst. More preferably, a Cu catalyst is employed, for example Cu, Cul, Cu2O, CuO, CuBr, or mixtures thereof. Preferably, the catalyst is CuI.
The catalyst is usually used in an amount of 1 mol % to 30 mol %, preferably 3 mol % to 27 mol %, more preferably 4 mol % to 25 mol %, most preferably 5 mol % to 20 mol %, based on the compound of formula I-3 respectively II-3.
In addition to the catalyst which is preferably present, at least one ligand is preferably present. Said ligand is preferably selected from the group consisting of
wherein R is for example OMe. The ligand is usually used in an amount of 5 mol % to 25 mol %, preferably 8 mol % to 20 mol %, more preferably 10 mol % to 17 mol %, most preferably 12 mol % to 16 mol %, based on the compound of formula I-3 respectively II-3. Preferably, the ligand is cis,trans-diaminocyclohexane.
The reaction is further preferably carried out in the presence of a base. Suitable bases are K3PO4, K2CO3, Na2CO3, Cs2CO3, NaH, NaOtBu, KOtBu, or mixtures thereof, preferably K3PO4, K2CO3, Na2CO3, Cs2CO3, or mixtures thereof. Preferably, the base is K3PO4.
The molar ratio of the base to R19—Br is usually 2:1 10 to 1:3, preferably 1.5:1 to 1:2.5, more preferably 1.3:1 to 1:2, most preferably 1.1:1 to 1:1.8.
The reaction temperature in the reaction step I-3 respectively II-3 mentioned above is usually 20° C. to 190° C., preferably 30° C. to 180° C., more preferably 60° C. to 170° C.
The reaction time in the reaction step I-3 respectively II-3 mentioned above is usually 10 minutes to 72 hours, preferably 2 hours to 48 hours, more preferably 3 hours to 24 hours.
The reaction pressure is not critical and usually atmospheric pressure.
The intermediates I-1 and II-1 are for example prepared as described in the PCT application PCT/IB2016/055872.
Base SkeletonThe synthesis of the compounds of formula (I) can be carried out in analogy to the synthesis of benzimidazolo[1,2-a]benzimidazoles mentioned in the relevant art.
The synthesis of
is described, for example, in Achour, Reddouane; Zniber, Rachid, Bulletin des Sociétés Chimiques Belges 96 (1987) 787-92, WO12130709, Org. Lett. 2012, 14, 02, 452, Eur. J. Org. Chem. 2014, 5986-5997, and RSC Advances 2014, 4, 21904-21908
N-ArylationThe introduction of the group —R9 (N-arylation) is generally carried out by reacting the base skeleton
with a group Hal-R9, wherein Hal is F, Cl, Br or I, preferably F, Br or I. Suitable groups R9 are mentioned before.
The nucleophilic aromatic substitution (N-arylation) of
with F—R9 is generally performed in the presence of a base (Angew. Chem. 2012, 124, 8136-8140, Angew. Chem. Int. Ed. 2008, 47, 8104-8107). Suitable bases are known to those skilled in the art and are preferably selected from the group consisting of alkali metal alkali metal and alkaline earth metal hydroxides such as NaOH, KOH, Ca(OH)2, alkali metal hydrides such as NaH, KH, alkali metal amides such as NaNH2, alkali metal or alkaline earth metal carbonates such as K2CO3 or Cs2CO3, alkaline metal phosphates such as K3PO4 alkaline metal fluorides such as KF, CsF and alkali metal alkoxides such as NaOMe, NaOEt. In addition, mixtures of the aforementioned bases are suitable. K2CO3 or Cs2CO3, K3PO4 are preferred.
The nucleophilic aromatic substitution (N-arylation) can be performed in solvent or in a melt. Preferably, the reaction is carried out in a solvent. Suitable solvents are, for example, (polar) aprotic solvents such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) or dimethylacetamide (DMA).
The reaction temperature is strongly dependent on the reactivity of the aryl fluoride. The reaction (N-arylation) is preferably carried out at a temperature of -10 to 220° C., more preferably 60 to 150° C.
Ullmann reaction (N-arylation) of
with Y—R1 (Y is Cl, Br, or I) generally performed in the presence of a base and a catalyst.
Reaction conditions for Ullmann reactions are, for example, described in Angew Chem Int Ed Engl., 48 (2009) 6954-71 WO14009317, WO12130709, J. Am. Chem. Soc. 131 (2009) 2009-2251, J. Org. Chem, 70 (2005) 5165.
Typically the Ullmann coupling of the compound of formula
with a compound of formula Y—R1 (Y is CI, Br, or I, especially Br, I very especially I) is done in the presence of copper, or a copper salt, such as, for example, Cul, CuBr, Cu2O, or CuO, and a ligand, such as, for example, L-proline, trans-cyclohexane-1,2-diamine (DACH), 1,10-phenanthroline in a solvent, such as, for example, dimethylsulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (NMP) and dioxane, or a solvent mixture. The reaction temperature is dependent on the reactivity of the starting materials, but is generally in the range of 25 to 200° C. If copper salt are used without a ligand the reaction temperatures are higher.
The N-arylation is, for example, disclosed in H. Gilman and D. A. Shirley, J. Am. Chem. Soc. 66 (1944) 888; D. Li et al., Dyes and Pigments 49 (2001) 181-186 and Eur. J. Org. Chem. (2007) 2147-2151.
Suitable base skeletons of the formula
are either commercially available (especially in the cases when X is S, O, NH), or can be obtained by processes known to those skilled in the art. Reference is made to WO2010079051 and EP1885818.
The halogenation of said base skeletons
(carbazole, dibenzofuran or dibe-zothiophene, which is unsubstituted or substituted) can be performed by methods known to those skilled in the art. Preference is given to brominating or iodinating in the 3 and 6 positions (dibromination, diiodation or mixed bromination/iodation) or in the 3 or 6 positions (monobromination, monoiodation) of the base skeleton in the case of carbazole, respectively in the 2 and 8 positions (dibromination, diiodation) or in the 2 or 8 positions (monobromination, monoiodation) of the base skeleton in the case of dibenzofuran and dibenzothiophene.
Optionally substituted dibenzofurans, dibenzothiophenes and carbazoles can be dibrominated in the 2,8 positions (dibenzofuran and dibenzothiophene) or 3,6 positions (carbazole) with bromine or NBS in glacial acetic acid or in chloroform. For example, the bromination with Br2 can be effected in glacial acetic acid or chloroform at low temperatures, e.g. 0° C. Suitable processes are described, for example, in M. Park, J. R. Buck, C. J. Rizzo, Tetrahedron, 54 (1998) 12707-12714 for X═NPh, and in W. Yang et al., J. Mater. Chem. 13 (2003) 1351 for X═S. In addition, 3,6-dibromocarbazole, 3,6-dibromo-9-phenylcarbazole, 2,8-dibromodibenzothiophene, 2,8-dibromodibenzofuran, 2-bromocarbazole, 3-bromodibenzothiophene, 3-bromodibenzofuran, 3-bromocarbazole, 2-bromodibenzothiophene and 2-bromodibenzofuran are commercially available.
Monobromination in the 4 position of dibenzofuran (and analogously for dibenzothiophene) is described, for example, in J. Am. Chem. Soc. 1984, 106, 7150. Dibenzofuran (dibenzothiophene) can be monobrominated in the 3 position by a sequence known to those skilled in the art, comprising a nitration, reduction and subsequent Sandmeyer reaction.
Monobromination in the 2 position of dibenzofuran or dibenzothiophene and monobromination in the 3 position of carbazole are effected analogously to the dibromination, with the exception that only one equivalent of bromine or NBS is added.
For the nucleophilic substitution, C1— or F-substituted dibenzofurans, dibenzothiophenes and carbazoles are preferred. The chlorination is described, inter alia, in J. Heterocyclic Chemistry, 34 (1997) 891-900, Org. Lett., 6 (2004) 3501-3504; J. Chem. Soc. [Section] C: Organic, 16 (1971) 2775-7, Tetrahedron Lett. 25 (1984) 5363-6, J. Org. Chem. 69 (2004) 8177-8182. The fluorination is described in J. Org. Chem. 63 (1998) 878-880 and J. Chem. Soc., Perkin Trans. 2, 5 (2002) 953-957.
Introduction of the
skeleton
The introduction of the
skeleton, can be affected, for example, by copper-catalyzed coupling (Ullmann reaction). Suitable reaction components and reaction conditions for carrying out the Ullmann reaction are mentioned above.
Alternatively, the introduction of the
skeleton, especially in cases, wherein the
skeleton is substituted, e.g. by a group
can be affected, for example, by Pd catalyzed coupling of diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes or carbazoles with halogenated aromatic groups, wherein the halogen is preferably I (Suzuki coupling).
An Example for a Suzuki coupling is shown in the example part of the present application:
Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and carbazoles can be readily prepared by an increasing number of routes. An overview of the synthetic routes is, for example, given in Angew. Chem. Int. Ed. 48 (2009) 9240-9261.
By one common route diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes, and carbazoles can be obtained by reacting halogenated dibenzofurans dibenzothiophenes and carbazoles with (Y1O)2B—B(OY1)2,
in the presence of a catalyst, such as, for example, [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), complex (Pd(Cl)2(dppf)), and a base, such as, for example, potassium acetate, in a solvent, such as, for example, dimethyl formamide, dimethyl sulfoxide, dioxane and/or toluene (cf. Prasad Appukkuttan et al., Synlett 8 (2003) 1204), wherein Y1 is independently in each occurrence a C1-C18alkylgroup and Y2 is independently in each occurrence a C2-C10alkylene group, such as —CY3Y4—CY5Y6—, or —CY7Y8—CY9Y10— CY11Y12—, wherein Y3, Y4, Y5, Y6, Y7, Y8, Y9, Y10, Y11 and Y12 are independently of each other hydrogen, or a C1-C18alkylgroup, especially —C(CH3)2C(CH3)2—, —C(CH3)2CH2C(CH3)2—, or —CH2C(CH3)2CH2—, and Y13 and Y14 are independently of each other hydrogen, or a C1-C18alkylgroup.
Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and carbazoles can also be prepared by reacting halogenated dibenzofurans, dibenzothiophenes and carbazoles with alkyl lithium reagents, such as, for example, n-butyl lithium, or t-buthyl lithium, followed by reaction with boronic esters, such as, for example, B(isopropoxy)3, B(methoxy)3, or
(cf. Synthesis (2000), 442-446).
Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and carbazoles can also be prepared by reacting dibenzofurans, dibenzothiophenes and carbazoles with lithium amides, such as, for example, lithium diisopropylamide (LDA) followed by reaction with boronic esters such as, for example, B(isopropoxy)3, B(methoxy)3, or
(J. Org. Chem. 73 (2008) 2176-2181).
In a further embodiment, the present invention concerns the following compounds, which are intermediates in the preparation of the compounds of formula (I):
-
- as well as
wherein the residues R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and R13 are described above.
Compounds of Formula (I) in Organic Electronics ApplicationsIt has been found that the compounds of the formula (I) are particularly suitable for use in applications in which charge carrier conductivity is required, especially for use in organic electronics applications, for example selected from switching elements such as organic transistors, e.g. organic FETs and organic TFTs, organic solar cells and organic light-emitting diodes (OLEDs).
The organic transistor generally includes a semiconductor layer formed from an organic layer with charge transport capacity; a gate electrode formed from a conductive layer; and an insulating layer introduced between the semiconductor layer and the conductive layer. A source electrode and a drain electrode are mounted on this arrangement in order thus to produce the transistor element. In addition, further layers known to those skilled in the art may be present in the organic transistor. The layers with charge transport capacity may comprise the compounds of formula (I).
The organic solar cell (photoelectric conversion element) generally comprises an organic layer present between two plate-type electrodes arranged in parallel. The organic layer may be configured on a comb-type electrode. There is no particular restriction regarding the site of the organic layer and there is no particular restriction regarding the material of the electrodes. When, however, plate-type electrodes arranged in parallel are used, at least one electrode is preferably formed from a transparent electrode, for example an ITO electrode or a fluorine-doped tin oxide electrode. The organic layer is formed from two sublayers, i.e. a layer with p-type semiconductor properties or hole transport capacity, and a layer formed with n-type semiconductor properties or charge transport capacity. In addition, it is possible for further layers known to those skilled in the art to be present in the organic solar cell. The layers with charge transport capacity may comprise the compounds of formula (I).
The compounds of the formula (I) being particularly suitable in OLEDs for use as matrix material in a light-emitting layer and/or as charge and/or exciton blocker material, i.e.as electron/exciton blocker material or as hole/exciton blocker material, and/or charge transport material, i.e. hole transport material or electron transport material, especially in combination with a phosphorescence emitter.
In the case of use of the inventive compounds of the formula (I) in OLEDs, OLEDs which have good efficiencies and a long lifetime and which can be operated especially at a low use and operating voltage are obtained. The inventive compounds of the formula (I) are suitable especially for use as matrix and/or charge transport, i.e. hole or electron transport, and/or charge blocker material, i.e. hole or electron blocker material, for green, red and yellow, preferably green and red, more preferably green emitters. Furthermore, the compounds of the formula (I) can be used as conductor/complementary materials in organic electronics applications selected from switching elements and organic solar cells. (In the sense of the present application, the terms matrix and host are used interchangeable).
In the emission layer or one of the emission layers of an OLED, it is also possible to combine an emitter material with at least one matrix material of the compound of the formula (I) and one or more, preferably one, further matrix materials (co-host). This may achieve a high quantum efficiency, low driving voltage and/or long lifetime of this device.
It is likewise possible that the compounds of the formula (I) are present in two or three of the following layers: in the light-emitting layer (preferably as matrix material), in the blocking layer (as charge blocker material) and/or in the charge transport layer (as charge transport material).
When a compound of the formula (I) is used as matrix (host) material in an emission layer and additionally as charge blocking material and/or as charge transport material, owing to the chemical identity or similarity of the materials, an improved interface between the emission layer and the adjacent material, which can lead to a decrease in the voltage with equal luminance and to an extension of the lifetime of the OLED. Moreover, the use of the same material as charge transport material and/or as charge blocker material and as matrix of an emission layer allows the production process of an OLED to be simplified, since the same source can be used for the vapor deposition process of the material of one of the compounds of the formula the compound of the formula (I).
Suitable structures of organic electronic devices, especially organic light-emitting diodes (OLED), are known to those skilled in the art and are specified below.
The present invention further provides an organic light-emitting diode (OLED) comprising an anode (a) and a cathode (i) and a light-emitting layer (e) arranged between the anode (a) and the cathode (i), and if appropriate at least one further layer selected from the group consisting of at least one blocking layer for holes/excitons, at least one blocking layer for electrons/excitons, at least one hole injection layer, at least one hole transport layer, at least one electron injection layer and at least one electron transport layer, wherein the at least one compound of the formula (I) is present in the light-emitting layer (e) and/or in at least one of the further layers. The at least one compound of the formula the compound of the formula (I) is preferably present in the light-emitting layer and/or the charge blocking layer and/or the charge transport layer.
In a preferred embodiment of the present invention, at least one compound of the formula the compound of the formula (I) is used as charge transport, i.e. electron transport or hole transport material. Examples of preferred compounds of the formula (I) are shown above.
In another preferred embodiment of the present invention, at least one compound of the formula the compound of the formula (I) is used as charge/exciton blocker material, i.e. as hole/exciton blocker material or electron/exciton blocker material. Examples of preferred compounds of the formula (I) are shown above.
The present application further relates to a light-emitting layer comprising at least one compound of the formula (I), preferably as host material or co-host material. Examples of preferred compounds of the formula (I) are shown above.
Structure of the Inventive OLEDThe inventive organic light-emitting diode (OLED) thus generally has the following structure: an anode (a) and a cathode (i) and a light-emitting layer (e) arranged between the anode (a) and the cathode (i).
The inventive OLED may, for example—in a preferred embodiment—be formed from the following layers:
1. Anode (a)
2. Hole transport layer (c)
3. Light-emitting layer (e)
4. Blocking layer for holes/excitons (f)
5. Electron transport layer (g)
6. Cathode (i)
Layer sequences different than the aforementioned structure are also possible, and are known to those skilled in the art. For example, it is possible that the OLED does not have all of the layers mentioned; for example, an OLED with layers (a) (anode), (e) (light-emitting layer) and (i) (cathode) is likewise suitable, in which case the functions of the layers (c) (hole transport layer) and (f) (blocking layer for holes/excitons) and (g) (electron transport layer) are assumed by the adjacent layers. OLEDs which have layers (a), (c), (e) and (i), or layers (a), (e), (f), (g) and (i), are likewise suitable. In addition, the OLEDs may have a blocking layer for electrons/excitons (d) between the hole transport layer (c) and the Light-emitting layer (e).
It is additionally possible that a plurality of the aforementioned functions (electron/exciton blocker, hole/exciton blocker, hole injection, hole conduction, electron injection, electron conduction) are combined in one layer and are assumed, for example, by a single material present in this layer. For example, a material used in the hole transport layer, in one embodiment, may simul-taneously block excitons and/or electrons.
Furthermore, the individual layers of the OLED among those specified above may in turn be formed from two or more layers. For example, the hole transport layer may be formed from a layer into which holes are injected from the electrode, and a layer which transports the holes away from the hole-injecting layer into the light-emitting layer. The electron transport layer may likewise consist of a plurality of layers, for example a layer in which electrons are injected by the electrode, and a layer which receives electrons from the electron injection layer and transports them into the light-emitting layer. These layers mentioned are each selected according to fac-tors such as energy level, thermal resistance and charge carrier mobility, and also energy difference of the layers specified with the organic layers or the metal electrodes. The person skilled in the art is capable of selecting the structure of the OLEDs such that it is matched opti-mally to the organic compounds used in accordance with the invention.
In a preferred embodiment the OLED according to the present invention comprises in this order: (a) an anode,
(b) optionally a hole injection layer,
(c) optionally a hole transport layer,
(d) optionally an exciton blocking layer
(e) an emitting layer,
(f) optionally a hole/exciton blocking layer
(g) optionally an electron transport layer,
(h) optionally an electron injection layer, and
(i) a cathode.
In a particularly preferred embodiment the OLED according to the present invention comprises in this order:
(a) an anode,
(b) optionally a hole injection layer,
(c) a hole transport layer,
(d) an exciton blocking layer
(e) an emitting layer,
(f) a hole/exciton blocking layer
(g) an electron transport layer, and
(h) optionally an electron injection layer, and
(i) a cathode.
The properties and functions of these various layers, as well as example materials are known from the art and are described in more detail below on basis of preferred embodiments.
Anode (a):The anode is an electrode which provides positive charge carriers. It may be composed, for example, of materials which comprise a metal, a mixture of different metals, a metal alloy, a metal oxide or a mixture of different metal oxides. Alternatively, the anode may be a conductive polymer. Suitable metals comprise the metals of groups 11, 4, 5 and 6 of the Periodic Table of the Elements, and also the transition metals of groups 8 to 10. When the anode is to be transparent, mixed metal oxides of groups 12, 13 and 14 of the Periodic Table of the Elements are generally used, for example indium tin oxide (ITO). It is likewise possible that the anode (a) comprises an organic material, for example polyaniline, as described, for example, in Nature, Vol. 357, pages 477 to 479 (Jun. 11, 1992). Preferred anode materials include conductive metal oxides, such as indium tin oxide (ITO) and indium zinc oxide (IZO), aluminum zinc oxide (AlZnO), and metals. Anode (and substrate) may be sufficiently transparent to create a bottom-emitting device. A preferred transparent substrate and anode combination is commercially available ITO (anode) deposited on glass or plastic (substrate). A reflective anode may be preferred for some top-emitting devices, to increase the amount of light emitted from the top of the device. At least either the anode or the cathode should be at least partly transparent in order to be able to emit the light formed. Other anode materials and structures may be used.
Hole Injection Layer (b):Generally, injection layers are comprised of a material that may improve the injection of charge carriers from one layer, such as an electrode or a charge generating layer, into an adjacent organic layer. Injection layers may also perform a charge transport function. The hole injection layer may be any layer that improves the injection of holes from anode into an adjacent organic layer. A hole injection layer may comprise a solution deposited material, such as a spin-coated polymer, or it may be a vapor deposited small molecule material, such as, for example, CuPc or MTDATA. Polymeric hole-injection materials can be used such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline, self-doping polymers, such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]-2,5-diyl) (Plexcore® OC Conducting Inks commercially available from Plextronics), and copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) also called PEDOT/PSS.
An example for a suitable hole injection material is:
(see also hole-transporting molecules).
Hole Transport Layer (c):Either hole-transporting molecules or polymers may be used as the hole transport material. Suitable hole transport materials for layer (c) of the inventive OLED are disclosed, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pages 837 to 860, 1996, US20070278938, US2008/0106190, US2011/0163302 (triarylamines with (di)benzothiophen/(di)benzofuran; Nan-Xing Hu et al. Synth. Met. 111 (2000) 421 (indolocarba-zoles), WO2010002850 (substituted phenylamine compounds) and WO2012/16601 (in particular the hole transport materials mentioned on pages 16 and 17 of WO2012/16601). Combination of different hole transport material may be used. Reference is made, for example, to WO2013/022419, wherein
constitute the hole transport layer.
Customarily used hole-transporting molecules are selected from the group consisting of
(4-phenyl-N-(4-phenylphenyl)-N-[4-[4-(N-[4-(4-phenyl-phenyl)phenyl]anilino)phenyl]phenyl]aniline),
(4-phenyl-N-(4-phenylphenyl)-N-[4-[4-(4-phenyl-N-(4-phenylphenyl)anilino)phenyl]phenyl]aniline),
(4-phenyl-N-[4-(9-phenylcarbazol-3-yl)phenyl]-N-(4-phenylphenyl)aniline),
(1,1′,3,3′-tetraphenylspiro[1,3,2-benzodiazasilole-2,2′-3a,7a-dihydro-1,3,2-benzodiazasilole]),
(N2,N2,N2′,N2′,N7,N7,N7′,N7′-octakis(p-tolyl)-9,9′-spirobi[fluorene]-2,2′,7,7′-tetramine), 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (α-NPD), N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine (TPD), 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine (ETPD), tetrakis(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA), α-phenyl-4-N,N-diphenylaminostyrene (TPS), p-(diethylamino)benzaldehyde diphenylhydrazone (DEH), tri-phenylamine (TPA), bis[4-(N,N-diethylamino)2-methylphenyl](4-methylphenyl)methane (MPMP), 1-phenyl-3-[p-(diethylamino)styryl]5-[p-(diethylamino)phenyl]pyrazoline (PPR or DEASP), 1,2-trans-bis(9H-carbazol9-yl)-cyclobutane (DCZB), N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB), fluorine compounds such as 2,2′,7,7′-tetra(N,N-di-tolyl)amino9,9-spirobifluorene (spiro-TTB), N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)9,9-spirobifluorene (spiro-NPB) and 9,9-bis(4-(N,N-bis-biphenyl-4-yl-amino)phenyl-9Hfluorene, benzidine compounds such as N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)benzidine and porphyrin compounds such as copper phthalocyanines. In addition, polymeric hole-injection materials can be used such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline, self-doping polymers, such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]-2,5-diyl) (Plexcore® OC Conducting Inks commercially available from Plextronics), and copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) also called PEDOT/PSS. Preferred examples of a material of the hole injecting layer are a porphyrin compound, an aromatic tertiary amine compound, or a styrylamine compound. Particularly preferable examples include an aromatic tertiary amine compound such as hexacyanohexaazatriphenylene (HAT).
The hole-transporting layer may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thicknesses more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device. Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, 2003, 359 (p-doped organic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No. 25, 2003, 4495 and Pfeiffer et al., Organic Electronics 2003, 4, 89-103 and K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev. 2007, 107, 1233. For example it is possible to use mixtures in the hole-transporting layer, in particular mixtures which lead to electrical p-doping of the hole-transporting layer. p-Doping is achieved by the addition of oxidizing materials. These mixtures may, for example, be the following mixtures: mixtures of the abovementioned hole transport materials with at least one metal oxide, for example MoO2, MoO3, WOE, ReO3 and/or V2O5, preferably MoO3 and/or ReO3, more preferably MoO3, or mixtures comprising the aforementioned hole transport materials and one or more compounds selected from 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), 2,5-bis(2-hydroxyethoxy)-7,7,8,8-tetracyanoquinodimethane, bis(tetra-n-butylammonium)tetracyanodiphenoquinodimethane, 2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene, 11,11,12,12-tetracyanonaphtho2,6-quinodimethane, 2-fluoro-7,7,8,8-tetracyanoquino-dimethane, 2,5-difluoro-7,7,8,8etracyanoquinodimethane, di-cyanomethylene-1,3,4,5,7,8-hexafluoro-6Hnaphthalen-2-ylidene)malononitrile (F6-TNAP), Mo(tfd)3 (from Kahn et al., J. Am. Chem. Soc. 2009, 131 (35), 12530-12531), compounds as described in EP1988587, US2008265216, EP2180029, US20100102709, WO2010132236, EP2180029 and quinone compounds as mentioned in EP2401254.
In addition to the materials mentioned above or as an alternative, the compound of formula (I) may be used as hole transport material.
Electron/Exciton Blocking Layer (d):Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer. An electron/exciton blocking layer (d) may be disposed between the first emitting layer (e) and the hole transport layer (c), to block electrons from emitting layer (e) in the direction of hole transport layer (c). Blocking layers may also be used to block excitons from diffusing out of the emissive layer.
Suitable metal complexes for use as electron/exciton blocker material are, for example, carbene complexes as described in WO2005/019373A2, WO2006/056418A2, WO2005/113704, WO2007/115970, WO2007/115981, WO2008/000727 and PCT/EP2014/055520. Explicit reference is made here to the disclosure of the WO applications cited, and these disclosures shall be considered to be incorporated into the content of the present application.
In addition to the materials mentioned above or as an alternative, the compound of formula (I) may be used as exciton/electron blocker material.
Emitting Layer (e)The light emitting layer is an organic layer having a light emitting function and is formed from one or more layers, wherein one of the layers comprises the host material and the light emitting material as described below.
Preferably, the light emitting layer of the inventive OLED comprises at least one compound of formula (I) as host material.
When the light emitting layer is composed of two or more layers, the light emitting layer or layers other than that mentioned above contains or contain a host material and a dopant material when a doping system is employed. The major function of the host material is to promote the recombination of electrons and holes and confine excitons in the light emitting layer. The dopant material causes the excitons generated by recombination to emit light efficiently.
In case of a phosphorescent device, the major function of the host material is to confine the excitons generated on the dopant in the light emitting layer.
The light emitting layer may be made into a double dopant layer, in which two or more kinds of dopant materials having high quantum yield are combinedly used and each dopant material emits light with its own color. For example, to obtain a yellow emission, a light emitting layer formed by co-depositing a host, a red-emitting dopant and a green-emitting dopant is used.
In a laminate of two or more light emitting layers, electrons and holes are accumulated in the interface between the light emitting layers, and therefore, the recombination region is localized in the interface between the light emitting layers, to improve the quantum efficiency.
The light emitting layer may be different in the hole injection ability and the electron injection ability, and also in the hole transporting ability and the electron transporting ability each being expressed by mobility.
The light emitting layer is formed, for example, by a known method, such as a vapor deposition method, a spin coating method, and LB method. Alternatively, the light emitting layer may be formed by making a solution of a binder, such as resin, and the material for the light emitting layer in a solvent into a thin film by a method such as spin coating.
The light emitting layer is preferably a molecular deposit film. The molecular deposit film is a thin film formed by depositing a vaporized material or a film formed by solidifying a material in the state of solution or liquid. The molecular deposit film can be distinguished from a thin film formed by LB method (molecular build-up film) by the differences in the assembly structures and higher order structures and the functional difference due to the structural differences.
The light-emitting layer (e) comprises at least one emitter material. In principle, it may be a fluo-rescence or phosphorescence emitter, suitable emitter materials being known to those skilled in the art. The at least one emitter material is preferably a phosphorescence emitter.
The emission wavelength of the phosphorescent dopant used in the light emitting layer is not particularly limited. In a preferred embodiment, at least one of the phosphorescent dopants used in the light emitting layer has the peak of emission wavelength of in general 430 nm or longer and 780 nm or shorter, preferably 490 nm or longer and 700 nm or shorter and more preferably 490 nm or longer and 650 nm or shorter. Most preferred are green emitter materials (490 nm to 570 nm).
The phosphorescent dopant (phosphorescent emitter material) is a compound which emits light by releasing the energy of excited triplet state and preferably a organometallic complex comprising at least one metal selected from Ir, Pt, Pd, Os, Au, Cu, Re, Rh and Ru and a ligand, alt-hough not particularly limited thereto as long as emitting light by releasing the energy of excited triplet state. A ligand having an ortho metal bond is preferred. In view of obtaining a high phosphorescent quantum yield and further improving the external quantum efficiency of electroluminescence device, a metal complex comprising a metal selected from Ir, Os, and Pt is preferred, with iridium complex, osmium complex, and platinum, particularly an ortho metallated complex thereof being more preferred, iridium complex and platinum complex being still more preferred, and an ortho metallated iridium complex being particularly preferred.
The compounds of the formula (I) can be used as the matrix in the light-emitting layer.
Suitable metal complexes for use in the inventive OLEDs, preferably as emitter material, are described, for example, in documents WO 02/60910 A1, US 2001/0015432 A1, US 2001/0019782 A1, US 2002/0055014 A1, US 2002/0024293 A1, US 2002/0048689 A1, EP 1 191 612 A2, EP 1 191 613 A2, EP 1 211 257 A2, US 2002/0094453 A1, WO 02/02714 A2, WO 00/70655 A2, WO 01/41512 A1, WO 02/15645 A1, WO 2005/019373 A2, WO 2005/113704 A2, WO 2006/115301 A1, WO 2006/067074 A1, WO 2006/056418, WO 2006121811 A1, WO 2007095118 A2, WO 2007/115970, WO 2007/115981, WO 2008/000727, WO2010129323, WO2010056669, WO10086089, US2011/0057559, WO2011/106344, US2011/0233528, WO2012/048266 and WO2012/172482.
Further suitable metal complexes are the commercially available metal complexes tris(2-phenylpyridine)iridium(III), iridium(III) tris(2-(4-tolyl)pyridinato-N,C2′), bis(2-phenylpyridine)(acetylacetonato)iridium(III), iridium(III) tris(1-phenylisoquinoline), iridium(III) bis(2,2′-benzothienyl)pyridinato-N,C3′)(acetylacetonate), tris(2-phenylquinoline)iridium(III), iridium(III) bis(2-(4,6-difluorophenyl)pyridinato-N,C2)picolinate, iridium(III) bis(1-phenylisoquinoline)(acetylacetonate), bis(2-phenylquinoline)(acetylacetonato)iridium(III), iridium(III) bis(di-benzo[f,h]quinoxaline)(acetylacetonate), iridium(III) bis(2-methyldi-benzo[f,h]quinoxaline)(acetylacetonate) and tris(3-methyl-1-phenyl-4-trimethylacetyl-5-pyrazolino)terbium(III), bis[1-(9,9-dimethyl-9H-fluoren-2-yl)isoquinoline](acetyl-acetonato)iridium(III), bis(2-phenylbenzothiazolato)(acetylacetonato)iridium(III), bis(2-(9,9-dihexylfluorenyl)-1-pyridine)(acetylacetonato)iridium(III), bis(2-benzo[b]thiophen-2-yl-pyridine)(acetylacetonato)iridium(l II).
In addition, the following commercially available materials are suitable: tris(dibenzoylacetonato)mono(phenanthroline)europium(III), tris(dibenzoylmethane)-mono(phenanthroline)europium(III), tris(dibenzoylmethane)mono(5-aminophenanthroline)-europium(III), tris(di-2-naphthoylmethane)mono(phenanthroline)europium(III), tris(4-bromobenzoylmethane)mono(phenanthroline)europium(III), tris(di(biphenyl)methane)-mono(phenanthroline)europium(III), tris(dibenzoylmethane)mono(4,7-diphenyl-phenanthroline)europium(III), tris(dibenzoylmethane)mono(4,7-di-methyl-phenanthroline)europium(III), tris(dibenzoylmethane)mono(4,7-dimethylphenanthrolinedisulfonic acid)europium(III) disodium salt, tris[di(4-(2-(2-ethoxyethoxy)ethoxy)benzoylmethane)]mono-(phenanthroline)europium(III) and tris[di[4-(2-(2-ethoxyethoxy)ethoxy)benzoylmethane)]mono(5-aminophenanthroline)europium(III), osmium(II) bis(3-(trifluoromethyl)-5-(4-tert-butylpyridyl)-1,2,4-triazolato)diphenylmethylphosphine, osmium(III) bis(3-(trifluoromethyl)-5-(2-pyridyl)-1,2,4-triazole)dimethylphenylphosphine, osmium(III) bis(3-(trifluoromethyl)-5-(4-tert-butylpyridyl)-1,2,4-triazolato)dimethylphenylphosphine, osmium(II) bis(3-(trifluoromethyl)-5-(2-pyridyl)-pyrazolato)dimethylphenylphosphine, tris[4,4′-di-tert-butyl(2,2′)-bipyridine]ruthenium(IIII), osmi-um(lII) bis(2-(9,9-dibutylfluorenyl)-1-isoquinoline(acetylacetonate).
Particularly suitable metal complexes are described in US2012223295, US2014367667, US2013234119, US2014001446, US2014231794, US2014008633, WO2012108388 and WO2012108389. The emitters mentioned in US2013234119, paragraph [0222], are exemplified. Selected emitters, especially red emitters, of said emitters mentioned in US2013234119, paragraph [0222], are:
Further suitable Emitters are mentioned in: MRS Bulletin, 2007, 32, 694:
Further suitable Emitters are mentioned in: WO2009100991:
Further suitable Emitters are mentioned in: WO2008101842:
Further suitable Emitters are mentioned in: US 20140048784, especially in paragraph [0159]:
Suitable phosphorescent blue emitters are specified in the following publications: WO2006/056418A2, WO2005/113704, WO2007/115970, WO2007/115981, WO2008/000727, WO2009050281, WO2009050290, WO2011051404, US2011/057559 WO2011/073149, WO2012/121936A2, US2012/0305894A1, WO2012/170571, WO2012/170461, WO2012/170463, WO2006/121811, WO2007/095118, WO2008/156879, WO2008/156879, WO2010/068876, US2011/0057559, WO2011/106344, US2011/0233528, WO2012/048266, WO2012/172482, PCT/EP2014/064054 and PCT/EP2014/066272.
The light emitting layer (e) comprises for example at least one carbene complex as phosphorescence emitter. Suitable carbene complexes are, for example, compounds of the formula
which are described in WO 2005/019373 A2, wherein the symbols have the following meanings:
M is a metal atom selected from the group consisting of Co, Rh, Ir, Nb, Pd, Pt, Fe, Ru, Os, Cr, Mo, W, Mn, Tc, Re, Cu, Ag and Au in any oxidation state possible for the respective metal atom; carbene is a carbene ligand which may be uncharged or monoanionic and monodentate, bidentate or tridentate, with the carbene ligand also being able to be a biscarbene or triscarbene ligand;
L is a monoanionic or dianionic ligand, which may be monodentate or bidentate;
K is an uncharged monodentate or bidentate ligand, preferably selected from the group consisting of phosphines; phosphonates and derivatives thereof, arsenates and derivatives thereof; phosphites; CO; pyridines; nitriles and conjugated dienes which form a π complex with M1;
n1 is the number of carbene ligands, where n1 is at least 1 and when n1>1 the carbene ligands in the complex of the formula I can be identical or different;
m1 is the number of ligands L, where m1 can be 0 or ≥1 and when m1>1 the ligands L can be identical or different;
o is the number of ligands K, where o can be 0 or ≥1 and when o>1 the ligands K can be identical or different;
where the sum n1+m1+o is dependent on the oxidation state and coordination number of the metal atom and on the denticity of the ligands carbene, L and K and also on the charge on the ligands, carbene and L, with the proviso that n1 is at least 1.
More preferred are metal-carbene complexes of the general formula
which are described in WO2011/073149, where M is Ir, or Pt,
n1 is an integer selected from 1, 2 and 3,
Y is NR51′, O, S or C(R25′)2,
A2′, A3′, A4′, and A5′ are each independently N or C, where 2 A′=nitrogen atoms and at least one carbon atom is present between two nitrogen atoms in the ring,
R51′ is a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms,
R52′, R53′, R54′ and R55′ are each, if A2′, A3′, A4′ and/or A5′ is N, a free electron pair, or, if A2′, A3′, A4′ and/or A5′ is C, each independently hydrogen, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms, group with donor or acceptor action, or
R53′ and R54′ together with A3′ and A4′ form an optionally substituted, unsaturated ring optionally interrupted by at least one further heteroatom and having a total of 5 to 18 carbon atoms and/or heteroatoms,
R56′, R57′, R58′ and R59′ are each independently hydrogen, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, cyclo-heteroalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms, group with donor or acceptor action, or
R56′ and R57′, R57′ and R58′ or R58′ and R59′, together with the carbon atoms to which they are bonded, form a saturated, unsaturated or aromatic, optionally substituted ring optionally interrupted by at least one heteroatom and having a total of 5 to 18 carbon atoms and/or heteroatoms, and/or
if A5′ is C, R55′ and R56′ together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, an aromatic unit, heteroaromatic unit and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which is optionally fused a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms,
R25′ is independently a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms,
K is an uncharged mono- or bidentate ligand,
L is a mono- or dianionic ligand, preferably monoanionic ligand, which may be mono- or bidentate,
m1 is 0, 1 or 2, where, when m1 is 2, the K ligands may be the same or different,
o1 is 0, 1 or 2, where, when o1 is 2, the L ligands may be the same or different.
The compound of formula XIV is preferably a compound of the formula:
Further suitable non-carbene emitter materials are mentioned below:
The compound of formula XIV is more preferably a compound (BE-1), (BE-2), (BE-7), (BE-12), (BE-16), (BE-64), or (BE-70). The most preferred phosphorescent blue emitters are compounds (BE-1) and (BE-12).
The homoleptic metal-carbene complexes may be present in the form of facial or meridional isomers or mixtures thereof, preference being given to the facial isomers.
Suitable carbene complexes of formula (XIV) and their preparation process are, for example, described in WO2011/073149.
The compounds of formula (I) the present invention can also be used as host for phosphorescent green emitters. Suitable phosphorescent green emitters are, for example, specified in the following publications: WO2006014599, WO20080220265, WO2009073245, WO2010027583, WO2010028151, US20110227049, WO2011090535, WO2012/08881, WO20100056669, WO20100118029, WO20100244004, WO2011109042, WO2012166608, US20120292600, EP2551933A1; U.S. Pat. No. 6,687,266, US20070190359, US20070190359, US20060008670; WO2006098460, US20110210316, WO2012053627; U.S. Pat. No. 6,921,915, US20090039776; JP2007123392 and European patent application no. 14180422.9.
Examples of suitable phosphorescent green emitters are shown below:
The emitter materials (dopants), preferably the phosphorescent emitter materials, may be used alone or in combination of two or more.
The content of the emitter materials (dopants), preferably the phosphorescent emitter materials, in the light emitting layer is not particularly limited and selected according to the use of the device, and preferably 0.1 to 70% by mass, and more preferably 1 to 30% by mass. If being 0.1% by mass or more, the amount of light emission is sufficient. If being 70% by mass or less, the concentration quenching can be avoided. The further component in the emitting layer is usually one or more host material, which is preferably present in an amount of 30 to 99.9% by mass, more preferably 70 to 99% by mass, wherein the sum of the emitter material(s) and the host material(s) is 100% by mass.
Host (Matrix) MaterialsThe light-emitting layer may comprise further components in addition to the emitter material. For example, a fluorescent dye may be present in the light-emitting layer in order to alter the emission color of the emitter material. In addition—in a preferred embodiment—a matrix material can be used. This matrix material may be a polymer, for example poly(N-vinylcarbazole) or polysilane. The matrix material may, however, be a small molecule, for example 4,4′-N,N′-dicarbazolebiphenyl (CDP=CBP) or tertiary aromatic amines, for example TCTA.
In the case that one or more phosphorescent emitter materials are used in the light emitting layer, one or more phosphorescent hosts are employed as host material. The phosphorescent host is a compound which confines the triplet energy of the phosphorescent dopant efficiently in the light emitting layer to cause the phosphorescent dopant to emit light efficiently.
In a preferred embodiment, the light-emitting layer is formed of at least one emitter material and of at least one of the matrix materials mentioned below—in one embodiment at least one compound of the formula (I) is used as matrix (host) material. In one embodiment, the light-emitting layer comprises at least one emitter material and at least two matrix materials, wherein one of the matrix materials is a compound of the formula (I) and the other matrix material(s) is/are used as co-host(s). Suitable other host materials than the compound of formula (I) (co-hosts) are mentioned below.
The compounds of the formula (I) are suitable as single host material as well as host material, together with one or more further host materials (co-host). Suitable further host materials are mentioned below. “Further host materials” means in the sense of the present application, host materials different from the compounds of formula (I). However, it is also possible to use two or more different compounds of formula (I) as host material in the light-emitting layer in an OLED of the present application.
In another preferred embodiment of the present invention, at least one compound of the formula (I) is used as host material. Examples of preferred compounds of formula (I) useful as host material are shown above.
In a more preferred embodiment, the light-emitting layer is formed from 0.1 to 70% by weight, preferably 1 to 30% by weight, of at least one of the aforementioned emitter materials and 30 to 99.9% by weight, preferably 70 to 99% by weight, of at least one of the matrix materials mentioned in the specification—in one embodiment at least one compound of the formula (I)—where the sum total of the emitter material and of the matrix material adds up to 100% by weight.
In a further more preferred embodiment, the light-emitting layer comprises a compound of formula (I) as matrix material, one further matrix material (co-host) and at least one emitter material. In said embodiment, the light-emitting layer is formed from 0.1 to 70% by weight, preferably 1 to 30% by weight, of the at least one emitter material and 30 to 99.9% by weight, preferably 70 to 99% by weight, of a compound of the formula (I) and the further matrix material, where the sum total of the at least one emitter material, the further matrix material and of the compound of formula (I) adds up to 100% by weight.
The content ratio of the compound of the formula (I) as first host material and the further matrix material as co-host in the light emitting layer is not particularly limited and may be selected accordingly, and the ratio of first host material:second host material (co-host) is preferably 1:99 to 99:1, more preferably 10:90 to 90:10, each based on mass.
Further suitable host materials, which may be small molecules or (co)polymers of the small molecules mentioned, are specified in the following publications: WO2007108459 (H-1 to H-37), preferably H-20 to H-22 and H-32 to H-37, most preferably H-20, H-32, H-36, H-37, WO2008035571 A1 (Host 1 to Host 6), JP2010135467 (compounds 1 to 46 and Host-1 to Host-39 and Host-43), WO2009008100 compounds No. 1 to No. 67, preferably No. 3, No. 4, No. 7 to No. 12, No. 55, No. 59, No. 63 to No. 67, more preferably No. 4, No. 8 to No. 12, No. 55, No. 59, No. 64, No. 65, and No. 67, WO2009008099 compounds No. 1 to No. 110, WO2008140114 compounds 1-1 to 1-50, WO2008090912 compounds OC-7 to OC-36 and the polymers of Mo-42 to Mo-51, JP2008084913H-1 to H-70, WO2007077810 compounds 1 to 44, preferably 1, 2, 4-6, 8, 19-22, 26, 28-30, 32, 36, 39-44, WO201001830 the polymers of monomers 1-1 to 1-9, preferably of 1-3, 1-7, and 1-9, WO2008029729 the (polymers of) compounds 1-1 to 1-36, WO20100443342 HS-1 to HS-101 and BH-1 to BH-17, preferably BH-1 to BH-17, JP2009182298 the (co)polymers based on the monomers 1 to 75, JP2009170764, JP2009135183 the (co)polymers based on the monomers 1-14, WO2009063757 preferably the (co)polymers based on the monomers 1-1 to 1-26, WO2008146838 the compounds a-1 to a-43 and 1-1 to 1-46, JP2008207520 the (co)polymers based on the monomers 1-1 to 1-26, JP2008066569 the (co)polymers based on the monomers 1-1 to 1-16, WO2008029652 the (co)polymers based on the monomers 1-1 to 1-52, WO2007114244 the (co)polymers based on the monomers 1-1 to 1-18, JP2010040830 the compounds HA-1 to HA-20, HB-1 to HB-16, HC-1 to HC-23 and the (co)polymers based on the monomers HD-1 to HD-12, JP2009021336, WO2010090077 the compounds 1 to 55, WO2010079678 the compounds H1 to H42, WO2010067746, WO2010044342 the compounds HS-1 to HS-101 and Poly-1 to Poly-4, JP2010114180 the compounds PH-1 to PH-36, US2009284138 the compounds 1 to 111 and H1 to H71, WO2008072596 the compounds 1 to 45, JP2010021336 the compounds H-1 to H-38, preferably H-1, WO2010004877 the compounds H-1 to H-60, JP2009267255 the compounds 1-1 to 1-105, WO2009104488 the compounds 1-1 to 1-38, WO2009086028, US2009153034, US2009134784, WO2009084413 the compounds 2-1 to 2-56, JP2009114369 the compounds 2-1 to 2-40, JP2009114370 the compounds 1 to 67, WO2009060742 the compounds 2-1 to 2-56, WO2009060757 the compounds 1-1 to 1-76, WO2009060780 the compounds 1-1 to 1-70, WO2009060779 the compounds 1-1 to 1-42, WO2008156105 the compounds 1 to 54, JP2009059767 the compounds 1 to 20, JP2008074939 the compounds 1 to 256, JP2008021687 the compounds 1 to 50, WO2007119816 the compounds 1 to 37, WO2010087222 the compounds H-1 to H-31, WO2010095564 the compounds HOST-1 to HOST-61, WO2007108362, WO2009003898, WO2009003919, WO2010040777, US2007224446, WO06128800, WO2012014621, WO2012105310, WO2012/130709 and European patent applications EP12175635.7, EP12185230.5 and EP12191408.9 (in particular page 25 to 29 of EP12191408.9).
The above-mentioned small molecules are more preferred than the above-mentioned (co)polymers of the small molecules.
Further suitable host materials, are described in WO2011137072 (for example,
best results are achieved if said compounds are combined with
WO2012048266 (for example,
The host materials mentioned above may be used in the OLED of the present invention a alone or in combination with the compound of formula (I) as host material. In this case, the compound of formula (I) is the host and the host materials mentioned above are the co-hosts.
Further examples of the compounds which are suitable as phosphorescent host, alone or in combination with the compound of formula (I) as host material, include a carbazole derivative, a triazole derivative, a oxazole derivative, an oxadiazole derivative, an imidazole derivative, a po-lyarylalkane derivative, a pyrazoline derivative, a pyrazolone derivative, a phenylenediamine derivative, an arylamine derivative, an amino-substituted chalcone derivative, a styrylanthra-cene derivative, a fluorenone derivative, a hydrazone derivative, a stilbene derivative, a silazane derivative, an aromatic tertiary amine compound, a styrylamine compound, an aromatic methyl-idene compound, a porphyrin compound, an anthraquinodimethane derivative, an anthrone derivative, a diphenylquinone derivative, a thiopyran dioxide derivative, a carbodiimide derivative, a fluorenylidenemethane derivative, a distyrylpyrazine derivative, a tetracarboxylic anhydride of fused ring such as naphthalene and perylene, a phthalocyanine derivative, a metal complex of 8-quinolinol derivative, metal phthalocyanine, metal complexes having a ligand such as benzoxazole and benzothiazole, an electroconductive oligomer, such as a polysilane compound, a poly(N-vinylcarbazole) derivative, an aniline copolymer, thiophene oligomer, and a polythiophene, and a polymer such as a polythiophene derivative, a polyphenylene derivative, a poly-phenylenevinylene derivative, and a polyfluorene derivative. These phosphorescent hosts may be used alone or in combination of two or more. Specific examples thereof are shown below:
Further suitable hosts, which are especially useful as co-host together with at least one compound of formula (I) are the hosts described in US2012223295, US2014367667, US2013234119, US2014001446, US2014231794, US2014008633, WO2012108388, WO2014009317 and WO2012108389, as well as the compounds of formula (I) described in the two EP applications filed at the same day as the present application, i.e. Sep. 30, 2015, with the title “Benzimidazolo[1,2-a]benzimidazole carrying triazine groups for Organic Light Emitting Diodes” and “Benzimidazolo[1,2-a]benzimidazole carrying benzofurane or benzothiophene groups for Organic Light Emitting Diodes”.
Especially preferred are the first and second host materials mentioned in US2013234119 and the compounds of formula (I) described in the two EP applications filed at the same day as the present application, i.e. Sep. 30, 2015, with the title “Benzimidazolo[1,2-a]benzimidazole carrying triazine groups for Organic Light Emitting Diodes” and “Benzimidazolo[1,2-a]benzimidazole carrying benzofurane or benzothiophene groups for Organic Light Emitting Diodes”.
The first host material mentioned in US2013234119 which is preferably used as co-host together with at least one compound of formula (I) in the light emitting layer of an OLED according to the present invention is represented by formula (A). The lifetime of an OLED is increased by combinedly using as a first host material at least one compound of formula (I) and as co-host the host material represented by formula (A) in the light emitting layer.
wherein
each of A1A and A2A independently represents an aryl group having 6 to 30 ring carbon atoms, which may be unsubstituted or substituted; or a heterocyclic group having 5 to 30 ring atoms, which may be unsubstituted or substituted;
A3A represents a divalent aryl group having 6 to 30 ring carbon atoms, which may be unsubstituted or substituted; or a divalent heterocyclic group having 5 to 30 ring atoms, which may be unsubstituted or substituted;
mA represents an integer of 0 to 3;
each of X1A to X8A and Y1A to Y8A independently represents N or CRa;
each of Ra independently represents a hydrogen atom, an aryl group having 6 to 30 ring carbon atoms, which may be unsubstituted or substituted; a heterocyclic group having 5 to 30 ring atoms, which may be unsubstituted or substituted; an alkyl group having 1 to 30 carbon atoms, which may be unsubstituted or substituted for example by E; a silyl group, which may be unsubstituted or substituted; a halogen atom, or a cyano group, provided that when two or more Ragroups exist, the Ra groups may be the same or different and one of X5A to X8A and one of Y1A to Y4A are bonded to each other via A3A; and
the formula (A) satisfies at least one of the flowing requirements (i) to (v);
(i) at least one of A1A and A2A represents a cyano-substituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms or a cyano-substituted heterocyclic group having 5 to 30 ring atoms;
(ii) at least one of X1A to X4A and Y5A to Y8A represents CRa, and at least one of Ra in X1A to X4A and Y5A to Y8A represents a cyano-substituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms or a cyano-substituted heterocyclic group having 5 to 30 ring atoms;
(iii) mA represents an integer of 1 to 3 and at least one of A3 represents a cyano-substituted divalent aromatic hydrocarbon group having 6 to 30 ring carbon atoms or a cyano-substituted divalent heterocyclic group having 5 to 30 ring atoms;
(iv) at least one of X5A to X8A and Y1A to Y4A represents CRa, and at least one of Ra in X5A to X8A and Y1A to Y4A represents a cyano-substituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms or a cyano-substituted heterocyclic group having 5 to 30 ring atoms; and
(v) at least one of X1A to X8A and Y1A to Y8A represents C—CN.
The cyano-substituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms and the cyano-substituted heterocyclic group having 5 to 30 ring atoms may be further substituted by a group other than the cyano group.
The subscript mA is preferably 0 to 2 and more preferably 0 or 1. When mA is 0, one of X5A to X8A and one of Y1A to Y4A are bonded to each other via a single bond.
In formula (A), the groups mentioned above have the following meanings:
The aromatic hydrocarbon group having 6 to 30 ring carbon atoms represented by A1A, A2A and Ra may be a non-condensed aromatic hydrocarbon group or a condensed aromatic hydrocarbon group. Specific examples thereof include phenyl group, naphthyl group, phenanthryl group, biphenyl group, terphenyl group, quaterphenyl group, fluoranthenyl group, triphenylenyl group, phenanthrenyl group, fluorenyl group, spirofluorenyl group, 9,9-diphenylfluorenyl group, 9,9′-spirobi[9H-fluorene]-2-yl group, 9,9-dimethylfluorenyl group, benzo[c]phenanthrenyl group, benzo[a]triphenylenyl group, naphtho[1,2-c]phenanthrenyl group, naphtho[1,2-a]triphenylenyl group, dibenzo[a,c]triphenylenyl group, and benzo[b]fluoranthenyl group, with phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, triphenylenyl group, fluorenyl group, spirobifluorenyl group, and fluoranthenyl group being preferred, and phenyl group, 1-naphthyl group, 2-naphthyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, phenanthrene-9-yl group, phenanthrene-3-yl group, phenanthrene-2-yl group, triphenylene-2-yl group, 9,9-dimethylfluorene-2-yl group, fluoranthene-3-yl group being more preferred.
Examples of the divalent aromatic hydrocarbon group having 6 to 30 ring carbon atoms represented by A3A include divalent residues of the above aromatic hydrocarbon groups having 6 to 30 ring carbon atoms.
The heterocyclic group having 5 to 30 ring atoms represented by A1A, A2A and Ra may be a non-condensed heterocyclic group or a condensed heterocyclic group. Specific examples thereof include the residues of pyrrole ring, isoindole ring, benzofuran ring, isobenzofuran ring, dibenzothiophene ring, isoquinoline ring, quinoxaline ring, phenanthridine ring, phenanthroline ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, indole ring, quinoline ring, acridine ring, pyrrolidine ring, dioxane ring, piperidine ring, morpholine ring, piperazine ring, carbazole ring, furan ring, thiophene ring, oxazole ring, oxadiazole ring, benzoxazole ring, thia-zole ring, thiadiazole ring, benzothiazole ring, triazole ring, imidazole ring, benzimidazole ring, pyran ring, dibenzofuran ring, and benzo[c]dibenzofuran ring, and the residues of derivatives of these rings, with the residues of dibenzofuran ring, carbazole ring, dibenzothiophene ring, and derivatives of these rings being preferred, and the residues of dibenzofuran-2-yl group, dibenzofuran-4-yl group, 9-phenylcarbazole-3-yl group, 9-phenylcarbazole-2-yl group, dibenzothiophene-2-yl group, and dibenzothiophene-4-yl group being more preferred.
Examples of the divalent heterocyclic group having 5 to 30 ring atoms represented by A3A include divalent residues of the above heterocyclic group having 5 to 30 ring atoms.
Examples of the alkyl group having 1 to 30 carbon atoms represented by Ra include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, neopentyl group, 1-methylpentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, and adamantyl group, with methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, cyclopentyl group, and cyclohexyl group being preferred.
Examples of the silyl group, which may be unsubstituted or substituted; represented by Ra include trimethylsilyl group, triethylsilyl group, tributylsilyl group, dimethylethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, dimethylisopropylsilyl group, dimethylpropylsilyl group, dimethylbutylsilyl group, dimethyltertiarybutylsilyl group, diethylisopropylsilyl group, phenyldimethylsilyl group, diphenylmethylsilyl group, diphenyltertiarybutylsilyl group, and triphenylsilyl group, with trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, and propyldimethylsilyl group being preferred.
Examples of the halogen atom represented by Ra include fluorine, chlorine, bromine, and iodine, with fluorine being preferred.
Also preferred as Ra is a hydrogen atom or an aryl group having 6 to 30 ring carbon atoms, which may be unsubstituted or substituted.
Examples of the optional substituent indicated by “substituted or unsubstituted” and “may be substituted” referred to above or hereinafter include a halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, an alkyl group having 1 to 20, preferably 1 to 6 carbon atoms, a cycloalkyl group having 3 to 20, preferably 5 to 12 carbon atoms, an alkoxyl group having 1 to 20, preferably 1 to 5 carbon atoms, a haloalkyl group having 1 to 20, preferably 1 to 5 carbon atoms, a haloalkoxyl group having 1 to 20, preferably 1 to 5 carbon atoms, an alkylsilyl group having 1 to 10, preferably 1 to 5 carbon atoms, an aromatic hydrocarbon group having 6 to 30, preferably 6 to 18 ring carbon atoms, an aryloxy group having 6 to 30, preferably 6 to 18 ring carbon atoms, an arylsilyl group having 6 to 30, preferably 6 to 18 carbon atoms, an aralkyl group having 7 to 30, preferably 7 to 20 carbon atoms, and a heteroaryl group having 5 to 30, preferably 5 to 18 ring atoms.
The optional substituent mentioned above may be further substituted by the optional group mentioned above.
Examples of the optional alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, neopentyl group, and 1-methylpentyl group.
Examples of the optional cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, and adamantyl group.
Examples of the optional alkoxyl group having 1 to 20 carbon atoms include those having an alkyl portion selected from the alkyl groups mentioned above.
Examples of the optional haloalkyl group having 1 to 20 carbon atoms include the alkyl groups mentioned above wherein the hydrogen atoms thereof are partly or entirely substituted by halogen atoms.
Examples of the optional haloalkoxyl group having 1 to 20 carbon atoms include the alkoxyl group mentioned above wherein the hydrogen atoms thereof are partly or entirely substituted by halogen atoms.
Examples of the optional alkylsilyl group having 1 to 10 carbon atoms include trimethylsilyl group, triethylsilyl group, tributylsilyl group, dimethylethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, dimethylisopropylsilyl group, dimethylpropylsilyl group, dimethylbutylsilyl group, dimethyltertiarybutylsilyl group, and diethylisopropylsilyl group.
Examples of the optional aryl group having 6 to 30 ring carbon atoms include those selected from the aryl groups mentioned above with respect to A1A, A2A and Ra.
Examples of the optional aryloxy group having 6 to 30 ring carbon atoms include those having an aryl portion selected from the aromatic hydrocarbon groups mentioned above.
Examples of the optional arylsilyl group having 6 to 30 carbon atoms include phenyldimethylsilyl group, diphenylmethylsilyl group, diphenyltertiarybutylsilyl group, and triphenylsilyl group.
Examples of the optional aralkyl group having 7 to 30 carbon atoms include benzyl group, 2-phenylpropane-2-yl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group, α-naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β-naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group, 2-β-naphthylisopropyl group, 1-pyrrolylmethyl group, 2-(1-pyrrolyl)ethyl group, p-methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group, and 1-chloro-2-phenylisopropyl group.
Examples of the optional heteroaryl group having 5 to 30 ring atoms include those selected from the heterocyclic groups mentioned above with respect to A1A, A2A and Ra.
The “carbon number of a to b” in the expression of “substituted or unsubstituted X group having carbon number of a to b” is the carbon number of the unsubstituted X group and does not include the carbon atom of the optional substituent.
The hydrogen atom referred to herein includes isotopes different from neutron numbers, i.e., light hydrogen (protium), heavy hydrogen (deuterium) and tritium.
In the host material represented by formula (A), the groups represented by formulae (a) and (b) are bonded to each other via -(A3)mA- at one of X5A to X8A and one of Y1A to Y4A. Specific examples of the bonding manner between formulae (a) and (b) are represented by X6A(A3A)mA-Y3A, X6A(A3A)mA-Y2A, X6A(A3A)mA-Y4A, X6A(A3A)mA-Y1A, X7A-(A3A)mA-Y3A, X5A-(A3A)mA-Y3A, X8A-(A3A)mA-Y3A, X7A-(A3A)mA-Y2A, X7A-(A3A)mA-Y4A, X7A-(A3A)mA-Y1A, X5A-(A3A)mA-Y2A, X8A-(A3A)mA- Y2A, X8A (A3A)mA-Y4A, X8A-(A3A)mA-Y1A, X5A-(A3A)mA-Y1A, and X5A-(A3A)mA-Y4A.
In preferred embodiments of the host material represented by formula (A), the bonding manner between formulae (a) and (b) are represented by X6A-(A3A)mA-Y3A, X6A-(A3A)mA-Y2A, or X7A-(A3A)mA-Y3A, namely the material for organic electroluminescence device is preferably represented by formula (II), (III), or (IV):
wherein X1A to X8A, Y1A to Y8A, A1A to A3A, and mA are the same as X1A to X8A, Y1A to Y8A, A1A to A3A, mA in formula (A), and each of formulae (II), (III), and (IV) satisfies at least one of the requirements (i) to (v) as specified in the definition of formula (A).
The host material represented by formula (A) satisfies at least one of the requirements (i) to (v), namely, the host material is a cyano group-introduced biscarbazole derivative having a group represented by formula (a) and a group represented by formula (b) which are linked to each other.
A3A of formula (A) preferably represents a single bond, a substituted or unsubstituted divalent monocyclic hydrocarbon group having 6 or less ring carbon atoms, or a substituted or unsubstituted divalent monocyclic heterocyclic group having 6 or less ring atoms.
Examples of the monocyclic hydrocarbon group having 6 or less ring carbon atoms represented by A3A include phenylene group, cyclopentenylene group, cyclopentadienylene group, cyclo-hexylene group, and cyclopentylene group, with phenylene group being preferred.
Examples of the monocyclic heterocyclic group having 6 or less ring atoms represented by A3Ainclude pyrrolylene group, pyrazinylene group, pyridinylene group, furylene group, and thio-phenylene group.
In a preferred embodiment of formulae (A), (II), (III), and (IV), mA is 0 and one of X5A to X8A and one of Y1A to Y4A are bonded to each other via a single bond; or A3A represents the substituted or unsubstituted monocyclic hydrocarbon group having 6 or less ring carbon atoms or the substituted or unsubstituted monocyclic heterocyclic group having 6 or less ring atoms. In more preferred embodiment, mA is 0 and one of X5A to X8A and one of Y1A to Y4A are bonded to each other via a single bond; or A3A represents a substituted or unsubstituted phenylene group.
The host material of formula (A) satisfies preferably at least one of the requirements (i) and (ii);
(i) at least one of A1A and A2A represents a cyano-substituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms or a cyano-substituted heterocyclic group having 5 to 30 ring atoms; and
(ii) at least one of X1A to X4A and Y5A to Y8A represents CRa, and at least one of Ra in X1A to X4A and Y5A to Y8A represents a cyano-substituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms or a cyano-substituted heterocyclic group having 5 to 30 ring atoms.
Namely, the host material of formula (A) is preferably any one of the compounds;
(1) satisfying the requirement (i), but not satisfying the requirements (ii) to (v);
(2) satisfying the requirement (ii), but not satisfying the requirements (i) and (iii) to (v); and
(3) satisfying both the requirements (i) and (ii), but not satisfying the requirements (iii) to (v).
The host material of formula (A) satisfying the requirement (i) and/or (ii) has a structure wherein the cyano group-containing aromatic hydrocarbon group or the cyano group-containing heterocyclic group is introduced to the terminal end of the central skeleton comprising the groups represented by formulae (a) and (b).
When the host material of formula (A) satisfies the requirement (i), at least one of A1A and A2A is preferably a cyano-substituted phenyl group, a cyano-substituted naphthyl group, a cyano-substituted phenanthryl group, a cyano-substituted dibenzofuranyl group, a cyano-substituted dibenzothiophenyl group, a cyano-substituted biphenyl group, a cyano-substituted terphenyl group, a cyano-substituted 9,9-diphenylfluorenyl group, a cyano-substituted 9,9′-spirobi[9H-fluorene]-2-yl group, a cyano-substituted 9,9′-dimethylfluorenyl group, or a cyano-substituted triphenylenyl group, and more preferably 3′-cyanobiphenyl-2-yl group, 3′-cyanobiphenyl-3-yl group, 3′-cyanobiphenyl-4-yl group, 4′-cyanobiphenyl-3-yl group, 4′-cyanobiphenyl-4-yl group, 4′-cyanobiphenyl-2-yl group, 6-cyanonaphthalene-2-yl group, 4-cyanonaphthalene-1-yl group, 7-cyanonaphthalene-2-yl group, 8-cyanodibenzofuran-2-yl group, 6-cyanodibenzofuran-4-yl group, 8-cyanodibenzothiophene-2-yl group, 6-cyanodibenzothiophene-4-yl group, 7-cyano-9-phenylcarbazole-2-yl group, 6-cyano-9-phenylcarbazole-3-yl group, 7-cyano-9,9-dimethylfluorene-2-yl group, or 7-cyanotriphenylene-2-yl group.
The host material of formula (A) wherein A1A is substituted by a cyano group and A2A is not substituted by a cyano group is preferred. In this case, the first host material which does not satisfy the requirement (ii) is more preferred.
When the host material of formula (A) satisfies the requirement (ii), at least one of X1A to X4A and Y5A to Y8A is preferably CRa, and one of Ra in X1A to X4A and Y5A to Y8A is preferably a cy-ano-substituted phenyl group, a cyano-substituted naphthyl group, a cyano-substituted phenanthryl group, a cyano-substituted dibenzofuranyl group, a cyano-substituted dibenzothiophenyl group, a cyano-substituted biphenyl group, a cyano-substituted terphenyl group, a cyano-substituted 9,9-diphenylfluorenyl group, a cyano-substituted 9,9′-spirobi[9H-fluorene]-2-yl group, a cyano-substituted 9,9′-dimethylfluorenyl group, or a cyano-substituted triphenylenyl group, and more preferably 3′-cyanobiphenyl-2-yl group, 3′-cyanobiphenyl-3-yl group, 3′-cyanobiphenyl-4-yl group, 4′-cyanobiphenyl-3-yl group, 4′-cyanobiphenyl-4-yl group, 4′-cyanobiphenyl-2-yl group, 6-cyanonaphthalene-2-yl group, 4-cyanonaphthalene-1-yl group, 7-cyanonaphthalene-2-yl group, 8-cyanodibenzofuran-2-yl group, 6-cyanodibenzofuran-4-yl group, 8-cyanodibenzothiophene-2-yl group, 6-cyanodibenzothiophene-4-yl group, 7-cyano-9-phenylcarbazole-2-yl group, 6-cyano-9-phenylcarbazole-3-yl group, 7-cyano-9,9-dimethylfluorene-2-yl group, or 7-cyanotriphenylene-2-yl group.
It is preferred for the host material of formula (A) to satisfy the requirement (ii), but not satisfy the requirement (i).
In formulae (A) and (II) to (IV), A1A and A2Aare preferably different from each other, and more preferably, A1A is substituted by a cyano group but A2A is not substituted by a cyano group. Namely, the host material of formula (A) is preferably structurally asymmetric.
The production method of the first host material is not particularly limited and it is produced according to a known method, for example, by a coupling reaction of a carbazole derivative and an aromatic halogenated compound in the presence of a copper catalyst described in Tetrahedron 40 (1984) 1435 to 1456 or a palladium catalyst described in Journal of American Chemical Society 123 (2001) 7727 to 7729.
Examples of the host material of formula (A) are mentioned in [0145] in US2013234119.
Examples for preferred host materials used as co-hosts mentioned in US2013234119 WO2012108388 and WO2014009317 are:
It is further possible to employ the compound of formula (I) to the present invention as host material in an OLED, preferably in the light emitting layer, together with at least one second host material described in US 2013234119, especially in paragraphs [0146] to [0195] in US 2013234119.
The second host material mentioned in US2013234119 which is preferably used as used co-host together with at least one compound of formula (I) in the light emitting layer of an OLED according to the present invention is represented by formula (KoH1).
Z1 represents a ring structure fused to the side a and represented by formula (KoH1-1) or (KoH 1-2), and
Z2 represents a ring structure fused to the side b and represented by formula (KoH1-1) or (KoH1-2), provided that at least one of Z1 and Z2 is represented by formula (KoH 1-1);
M1 represents a nitrogen-containing heteroaryl group having 5 to 30 ring atoms, which may be unsubstituted or substituted for example by G;
L1′ represents a single bond, a divalent aromatic hydrocarbon group having 6 to 30 ring carbon atoms which may be unsubstituted or substituted for example by G, a divalent heterocyclic group having 5 to 30 ring atoms which may be unsubstituted or substituted for example by G, a cycloalkylene group having 5 to 30 ring atoms, or a group in which the preceding groups are directly linked to each other; and
k represents 1 or 2.
In formula (KoH1-1), a side c is fused to the side a or b of formula (KoH1).
In formula (KoH1-2), any one of sides d, e and f is fused to the side a or b of formula (KoH1).
In formulae (KoH1-1) and (KoH 1-2):
X11 represents a sulfur atom, an oxygen atom, NR77, or C(R78)(R79); and each of R51 to R54 and R55 to R58 independently represents a hydrogen atom, a heavy hydrogen atom, a halogen atom, a cyano group, an aryl group having 6 to 30 ring carbon atoms, which may be unsubstituted or substituted for example by G, a cycloalkylene group having 5 to 30 ring atoms, a heterocyclic group having 5 to 30 ring atoms, which may be unsubstituted or substituted for example by G, an alkyl group having 1 to 30 carbon atoms, which may be unsubstituted or substituted for example by E, an alkenyl group having 2 to 30 carbon atoms, which may be unsubstituted or substituted for example by E, an alkynyl group having 2 to 30 carbon atoms, which may be unsubstituted or substituted for example by G, an alkylsilyl group having 3 to 30 carbon atoms, which may be unsubstituted or substituted for example by E, an arylsilyl group having 6 to 30 ring carbon atoms, which may be unsubstituted or substituted for example by G, an alkoxy group having 1 to 30 carbon atoms, which may be unsubstituted or substituted for example by E, an aralkyl group having 6 to 30 ring carbon atoms, which may be unsubstituted or substituted for example by G, or an aryloxy group having 6 to 30 ring carbon atoms, which may be unsubstituted or substituted for example by G, provided that adjacent groups of R51 to R54 and R55 to R58 may be bonded to each other to form a ring;
R77 is a C6-C24aryl group, which can optionally be substituted by G, or a C1-C24heteroaryl group, which can optionally be substituted by G;
R78, R79 is a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G, or a C1-C24heteroaryl group, which can optionally be substituted by G;
E is —OR69, —SR69, —NR65R66, —COR68, —COOR67, —CONR65R66, —CN, —Si(R70)3 or halogen. E is preferably —OR69; —SR69; —NR65R66; —COR68; —COOR67; —CON65R66; or —CN; wherein R65, R66, R67, R68 and R69 are preferably independently of each other C1-C18alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-C14aryl, such as phenyl, tolyl, naphthyl, triphenylyl or biphenylyl;
G is E, or a C1-C24alkyl group, a C6-C30aryl group, a C6-C30aryl group, which is substituted by F, C1-C24alkyl, or C1-C24alkyl which is interrupted by O; a C2-C60heteroaryl group, or a C2-C60heteroaryl group, which is substituted by F, C1-C18alkyl, or C1-C18alkyl which is interrupted by O. G is preferably—OR69, —SR69, —NR65R66; a C1-C18alkyl group, a C6-C18aryl group, a C6-C18aryl group, which is substituted by F, or C1-C18alkyl; a C2-C24heteroaryl group, or a C2-C24heteroaryl group, which is substituted by F, or C1-C18alkyl; wherein R65, R66 and R69 are independently of each other C1-C18alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-C14aryl, such as phenyl, tolyl, naphthyl, or biphenylyl. More preferably, G is a C6-C18aryl group like phenyl, tolyl, triphenylyl or biphenylyl, or a C6-C24heteroaryl group like dibenzothiophenylyl, dibenzofuranyl, pyridyl, triazinyl, pyrimidinyl, azatriphenylyl, azadibenzofuryl, azadibenzothiophenyl, azacarbazolyl, quinolonyl, isoquinolinyl, quinoxalinyl, quinazolinyl, phenanthrolinyl, phenanthridinyl, benzo[h]quinolonyl, benz[h]isoquinolinyl, benzo[f]isoquinolinyl, benzo[f]quinolinyl, benzo[h]quinazolinyl, benzo[f]quinazolinyl, dibenzo[f,h]quinolonyl, dibenzo[f,h]isoquinolonyl, dibenzo[f,h]quinoxalinyl or dibenzo[f,h]quinazolinyl.
Examples for preferred second host materials used as co-hosts mentioned in US2013234119 are:
Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer. The hole blocking layer may be disposed between the emitting layer (e) and electron transport layer (g), to block holes from leaving layer (e) in the direction of electron transport layer (g). Blocking layers may also be used to block excitons from diffusing out of the emissive layer.
Additional hole blocker materials typically used in OLEDs are 2,6-bis(N-carbazolyl)pyridine (mCPy), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproin, (BCP)), bis(2-methyl-8-quinolinato)-4-phenylphenylato)aluminum(III) (BAIq), phenothiazine S,S-dioxide derivates and 1,3,5-tris(N-phenyl-2-benzylimidazolyl)benzene) (TPBI), TPBI also being suitable as electron-transport material. Further suitable hole blockers and/or electron conductor materials are 2,2′,2″-(1,3,5-benzenetriyl)tris(1-phenyl-1-H-benzimidazole), 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole, 8-hydroxyquinolinolatolithium, 4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole, 1,3-bis[2-(2,2′-bipyridin-6-yl)-1,3,4-oxadiazo-5-yl]benzene, 4,7-diphenyl-1,10-phenanthroline, 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole, 6,6′-bis[5-(biphenyl-4-yl)-1,3,4-oxadiazo-2-yl]-2,2′-bipyridyl, 2-phenyl-9,10-di(naphthalene-2-yl)anthracene, 2,7-bis[2-(2,2′-bipyridin-6-yl)-1,3,4-oxadiazo-5-yl]-9,9-dimethylfluorene, 1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl]benzene, 2-(naphthalene-2-yl)-4,7-diphenyl-1,10-phenanthroline, tris(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane, 2,9-bis(naphthalene-2-yl)-4,7-diphenyl-1,10-phenanthroline, 1-methyl-2-(4-(naphthalene-2-yl)phenyl)-1H-imidazo[4,5-f][1,10]-phenanthroline. In a further embodiment, it is possible to use compounds which comprise aromatic or heteroaromatic rings joined via groups comprising carbonyl groups, as disclosed in WO2006/100298, disilyl compounds selected from the group consisting of disilylcarbazoles, disilylbenzofurans, disilylbenzothiophenes, disilylbenzophospholes, disilylbenzothiophene S-oxides and disilylbenzothiophene S,S-dioxides, as specified, for example, in PCT applications WO2009/003919 and WO2009003898 and disilyl compounds as disclosed in WO2008/034758, as a blocking layer for holes/excitons (f).
In another preferred embodiment compounds (SH-1), (SH-2), (SH-3), SH-4, SH-5, SH-6, (SH-7), (SH-8), (SH-9), (SH-10) and (SH-11) may be used as hole/exciton blocking materials.
In addition to the materials mentioned above or as an alternative, the compound of formula (I) may be used as hole/exciton blocker material.
Electron Transport Layer (g):Electron transport layer may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity.
The compound of the formula (I) is suitable as electron transport material, either alone or in combination with one or more of the electron transport materials mentioned below.
Further suitable electron-transporting materials for layer (g) of the inventive OLEDs, which may be used in combination with the compound of formula (I) or in absence of the compound of formula (I) as electron transport material, comprise metals chelated with oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum (Alq3), compounds based on phenanthroline such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA=BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), 2,4,7,9-tetraphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline (DPA) or phenanthroline derivatives disclosed in EP1786050, in EP1970371, or in EP1097981, and azole compounds such as 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) and 3-(4-biphenylyl)-4phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ).
Further suitable electron transport materials, which may be used in combination with the compound of formula (I) or in absence of the compound of formula (I) as electron transport material, are mentioned in Abhishek P. Kulkarni, Christopher J. Tonzola, Amit Babel, and Samson A. Jenekhe, Chem. Mater. 2004, 16, 4556-4573; G. Hughes, M. R. Bryce, J. Mater. Chem. 2005, 15, 94-107 and Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010 (ETM, HTM).
It is likewise possible to use mixtures of at least two materials in the electron-transporting layer, in which case at least one material is electron-conducting. Preferably, in such mixed electron-transport layers, at least one phenanthroline compound is used, preferably BCP, or at least one pyridine compound according to the formula (XVI) below, preferably a compound of the formula (XVIa) below. More preferably, in mixed electron-transport layers, in addition to at least one phenanthroline compound, alkaline earth metal or alkali metal hydroxyquinolate complexes, for example Liq, are used. Suitable alkaline earth metal or alkali metal hydroxyquinolate complexes are specified below (formula XVII). Reference is made to WO2011/157779.
The electron-transport layer may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thicknesses more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device. Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, No. 1, 1 Jul. 2003 (p-doped organic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No. 25, 23 Jun. 2003 and Pfeiffer et al., Organic Electronics 2003, 4, 89-103 and K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev. 2007, 107, 1233. For example, it is possible to use mixtures which lead to electrical n-doping of the electron-transport layer. n-Doping is achieved by the addition of reducing materials. These mixtures may, for example, be mixtures of the abovementioned electron transport materials with alkali/alkaline earth metals or alkali/alkaline earth metal salts, for example Li, Cs, Ca, Sr, Cs2CO3, with alkali metal complexes, for example 8-hydroxyquinolatolithium (Liq), and with Y, Ce, Sm, Gd, Tb, Er, Tm, Yb, Li3N, Rb2CO3, dipotassi-um phthalate, W(hpp)4 from EP1786050, or with compounds described in EP1837926B1, EP1837927, EP2246862 and WO2010132236.
In a preferred embodiment, the electron-transport layer comprises at least one compound of the general formula (XVII)
in which
R32′ and R33′ are each independently F, C1-C8-alkyl, or C6-C14-aryl, which is optionally substituted by one or more C1-C8-alkyl groups, or
two R32′ and/or R33′ substituents together form a fused benzene ring which is optionally substituted by one or more C1-C8-alkyl groups;
a and b are each independently 0, or 1, 2 or 3,
M1 is an alkaline metal atom or alkaline earth metal atom,
p is 1 when M1 is an alkali metal atom, p is 2 when M1 is an earth alkali metal atom.
A very particularly preferred compound of the formula (XVII) is
which may be present as a single species, or in other forms such as LigQg in which g is an integer, for example Li6Q6. Q is an 8-hydroxyquinolate ligand or an 8-hydroxyquinolate derivative.
In a further preferred embodiment, the electron-transport layer comprises at least one compound of the formula (XVI),
in which
R34″, R35″, R36″, R37″, R34′, R35′, R36′ and R37′ are each independently H, C1-C18-alkyl, C1-C18-alkyl which is substituted by E′ and/or interrupted by D′, C6-C24-aryl, C6-C24-aryl which is substituted by G′, C2-C20-heteroaryl or C2-C20-heteroaryl which is substituted by G′,
Q is an arylene or heteroarylene group, each of which is optionally substituted by G′;
D′ is —CO—; —COO—; —S—; —SO—; —SO2—; —O—; —NR40′—; —SiR45′ R46′—; —POR47′—; —CR38′═CR39′—; or —C≡C—;
E′ is —OR44′; —SR44′; —NR40′R41′; —COR43′; —COOR42′; —CONR40′R41′; —CN; or F;
G′ is E′, C1-C18-alkyl, C1-C18-alkyl which is interrupted by D′, C1-C18-perfluoroalkyl, C1-C18-alkoxy, or C1-C18-alkoxy which is substituted by E′ and/or interrupted by D′, in which
R38′ and R39′ are each independently H, C6-C18-aryl; C6-C18-aryl which is substituted by C1-C18-alkyl or C1-C18-alkoxy; C1-C18-alkyl; or C1-C18-alkyl which is interrupted by —O—;
R40′ and R41′ are each independently C6-C18-aryl; C6-C18-aryl which is substituted by C1-C18-alkyl or C1-C18-alkoxy; C1-C18-alkyl; or C1-C18-alkyl which is interrupted by —O—; or
R40′ and R41′ together form a 6-membered ring;
R42′ and R43′ are each independently C6-C18-aryl; C6-C18-aryl which is substituted by C1-C18-alkyl or C1-C18-alkoxy; C1-C18-alkyl; or C1-C18-alkyl which is interrupted by —O—,
R44′ is C6-C18-aryl; C6-C18-aryl which is substituted by C1-C18-alkyl or C1-C18-alkoxy; C1-C18-alkyl; or C1-C18-alkyl which is interrupted by —O—,
R45′ and R46′ are each independently C1-C18-alkyl, C6-C18-aryl or C6-C18-aryl which is substituted by C1-C18-alkyl,
R47′ is C1-C18-alkyl, C6-C18-aryl or C6-C18-aryl which is substituted by C1-C18-alkyl.
Preferred compounds of the formula (XVI) are compounds of the formula (XVIa)
in which Q is:
R48′ is H or C1-C18-alkyl and
R48″ is H, C1-C18-alkyl or
Particular preference is given to a compound of the formula
In a further, very particularly preferred embodiment, the electron-transport layer comprises a compound Liq and a compound ETM-2.
In a preferred embodiment, the electron-transport layer comprises at least one compound of the formula (XVII) in an amount of 99 to 1% by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, and at least one compound of the formula (XVI) in an amount of 1 to 99% by weight, preferably 25 to 75% by weight, more preferably about 50% by weight, where the amount of the compounds of the formulae (XVII) and the amount of the compounds of the formulae (XVI) adds up to a total of 100% by weight.
The preparation of the compounds of the formula (XVI) is described in J. Kido et al., Chem. Commun. (2008) 5821-5823, J. Kido et al., Chem. Mater. 20 (2008) 5951-5953 and JP2008/127326, or the compounds can be prepared analogously to the processes disclosed in the aforementioned documents.
It is likewise possible to use mixtures of alkali metal hydroxyquinolate complexes, preferably Liq, and dibenzofuran compounds in the electron-transport layer. Reference is made to WO2011/157790. Dibenzofuran compounds A-1 to A-36 and B-1 to B-22 described in WO2011/157790 are preferred, wherein dibenzofuran compound
(A-10; =ETM-1) is most preferred.
In a preferred embodiment, the electron-transport layer comprises Liq in an amount of 99 to 1% by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, and at least one dibenzofuran compound in an amount of 1 to 99% by weight, preferably 25 to 75% by weight, more preferably about 50% by weight, where the amount of Liq and the amount of the dibenzofuran compound(s), especially ETM-1, adds up to a total of 100% by weight.
In a preferred embodiment, the electron-transport layer comprises at least one phenanthroline derivative and/or pyridine derivative.
In a further preferred embodiment, the electron-transport layer comprises at least one phenanthroline derivative and/or pyridine derivative and at least one alkali metal hydroxyquinolate complex.
In a further preferred embodiment, the electron-transport layer comprises at least one of the dibenzofuran compounds A-1 to A-36 and B-1 to B-22 described in WO2011/157790, especially ETM-1.
In a further preferred embodiment, the electron-transport layer comprises a compound described in WO2012/111462, WO2012/147397, WO2012014621, such as, for example, a compound of formula
US2012/0261654, such as, for example, a compound of formula
and WO2012/115034, such as for example, such as, for example, a compound of formula
A further suitable electron transport material is:
The electron injection layer may be any layer that improves the injection of electrons into an adjacent organic layer.
The compound of the formula (I) is suitable as electron injection material, either alone or in combination with one or more of the electron injection materials mentioned below.
Further lithium-comprising organometallic compounds such as 8-hydroxyquinolatolithium (Liq), CsF, NaF, KF, Cs2CO3 or LiF may be applied between the electron transport layer (g) and the cathode (i) as an electron injection layer (h) in order to reduce the operating voltage.
Cathode (i):The cathode (i) is an electrode which serves to introduce electrons or negative charge carriers. The cathode may be any metal or nonmetal which has a lower work function than the anode. Suitable materials for the cathode are selected from the group consisting of alkali metals of group 1, for example Li, Cs, alkaline earth metals of group 2, metals of group 12 of the Periodic Table of the Elements, comprising the rare earth metals and the lanthanides and actinides. In addition, metals such as aluminum, indium, calcium, barium, samarium and magnesium, and combinations thereof, may be used.
In general, the different layers, if present, have the following thicknesses:
anode (a): 500 to 5000 Å (ångström), preferably 1000 to 2000 Å;
hole injection layer (b): 50 to 1000 Å, preferably 200 to 800 Å,
hole-transport layer (c): 50 to 1000 A, preferably 100 to 800 A,
exciton blocking layer (d): 10 to 500 A, preferably 50 to 100 A,
light-emitting layer (e): 10 to 1000 A, preferably 50 to 600 A,
hole/exciton blocking layer (f): 10 to 500 A, preferably 50 to 100 A,
electron-transport layer (g): 50 to 1000 A, preferably 200 to 800 A,
electron injection layer (h): 10 to 500 A, preferably 20 to 100 A,
cathode (i): 200 to 10 000 A, preferably 300 to 5000 A.
The person skilled in the art is aware (for example on the basis of electrochemical studies) of how suitable materials have to be selected. Suitable materials for the individual layers are known to those skilled in the art and are disclosed, for example, in WO 00/70655.
In addition, it is possible that some of the layers used in the inventive OLED have been surface-treated in order to increase the efficiency of charge carrier transport. The selection of the materials for each of the layers mentioned is preferably determined by obtaining an OLED with a high efficiency and lifetime.
The inventive OLED can be produced by methods known to those skilled in the art. In general, the inventive OLED is produced by successive vapor deposition of the individual layers onto a suitable substrate. Suitable substrates are, for example, glass, inorganic semiconductors or polymer films. For vapor deposition, it is possible to use customary techniques, such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD) and others. In an alternative process, the organic layers of the OLED can be applied from solutions or disper-sions in suitable solvents, employing coating techniques known to those skilled in the art.
Use of the compounds of the formula (I) in at least one layer of the OLED, preferably in the light-emitting layer (preferably as a matrix material), in a charge transport layer, i.e. electron transport layer or hole transport layer, preferably electron transport layer and/or in the electron injection layer makes it possible to obtain OLEDs with high efficiency and with low use and operating voltage. Frequently, the OLEDs obtained by the use of the compounds of the formula (I) additionally have high lifetimes. The efficiency of the OLEDs can additionally be improved by optimizing the other layers of the OLEDs. For example, high-efficiency cathodes such as Ca or Ba, if appropriate in combination with an intermediate layer of LiF, can be used. Moreover, additional layers may be present in the OLEDs in order to adjust the energy level of the different layers and to facilitate electroluminescence.
The OLEDs may further comprise at least one second light-emitting layer. The overall emission of the OLEDs may be composed of the emission of the at least two light-emitting layers and may also comprise white light.
The OLEDs can be used in all apparatus in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile visual display units and illumination units. Stationary visual display units are, for example, visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations and information panels. Mobile visual display units are, for example, visual display units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains. Further devices in which the inventive OLEDs can be used are, for example, keyboards; items of clothing; furniture; wallpaper. In addition, the present invention relates to a device selected from the group consisting of stationary visual display units such as visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations, information panels, and mobile visual display units such as visual display units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains; illumination units; keyboards; items of clothing; furniture; wallpaper, comprising at least one inventive organic light-emitting diode or at least one inventive light-emitting layer.
The following examples are included for illustrative purposes only and do not limit the scope of the claims. Unless otherwise stated, all parts and percentages are by weight.
EXAMPLES1,4-difluoro-2,5-dinitrobenzene was synthesized according known literature procedure (US20130237725). 3-phenyl-1H-benzimidazol-2-one was synthesized according known literature procedure (reaction of 1,10-carbonyldiimidazole with N2-phenylbenzene-1,2-diamine; Bioorganic and Medicinal Chemistry Letters, 2008, 18, 6067).
Example 1a.) 7.36 g (35.0 mmol) of 3-phenyl-1H-benzimidazol-2-one and 1.40 g (35 mmol) of NaH were mixed together in DMF (110 mL) at 0° C. for 10 min. Then, 3.57 g (17.5 mmol) of 1,4-difluoro-2,5-dinitrobenzene were added by portion. The mixture was stirred 2h at 0° C., precipitated in water and filtrated to yield 9.12 g of 1-1 as a yellow powder [Purity=94% (HPLC)] which was used directly as it is for the next step.
Mass [M+1]=584.4
b.) 8.76 g (15.0 mmol) of 1-1 and 1.00 g of Pd/C 10% were mixed in 125 mL of 5:1 THF:EtOH at 50° C. under 5 bar of dihydrogen for 12h. The mixture was then filtrated, the solvent evaporated and the resulting powder was recrystallized several times from THF to yield 5.58 g of 1-2 [Purity=98.0% (HPLC)] as a yellow powder.
Mass [M+1]=525.2
c.) 5.30 g (10.1 mmol) of 1-2 and 35 g of polyphosphoric acid were mixed together at 240° C. for 6h. The dark brown mixture was then poured into 400 mL of water, filtrated and washed several times with water and MeOH. The product was recrystallized in DMSO then NMP and sublimed 3 times to yield 1.69 g of 1 [Purity=99.79% (HPLC)] as a slightly yellow crystal.
Mass [M+1]=489.4
Example 2a.) 15.72 g (74.8 mmol) of 3-phenyl-1H-benzimidazol-2-one, 6.94 g (34.0 mmol) of 1,3-difluoro-4,6-dinitrobenzene and 28.87 g (136 mmol) of K3PO4 were mixed together in NMP (200 mL) at 0° C. for 2h. The mixture was then stirred 2h at room temperature and precipitated in water filtrated to yield 19.44 g of 2-1 as a yellow powder [Purity=85% (H PLC)] which was used directly as it is for the next step.
Mass [M+1]=584.2
b.) 4.38 g (7.5 mmol) of 2-1 and 500 mg of Pd/C 10% were mixed in 60 mL of 3:1 THF:EtOH at 50° C. under 5 bar of dihydrogen for 2h. The mixture was then filtrated, the solvent is evaporated and the resulting powder was purified by chromatography (SiO2, gradient: toluene/THF) to yield 2.12 g of 2-2 [Purity=99.0% (HPLC)] as a white powder.
Mass [M+1]=525.3
c.) 9.11 g (17.4 mmol) of 2-2 and 75 g of polyphosphoric acid were mixed together at 230° C. for 6h. The dark brown mixture was then poured into 650 mL of water, filtrated and washed several times with water and MeOH. The product was recrystallized twice in DMSO, washed with MeOH and sublimed twice. It was again recrystallized in DMSO and sublimed to yield 2.97 g of 2 [Purity 25=99.91% (H PLC)] as a white crystal.
Mass [M+1]=489.4
1H NMR (400 MHz, DMSO): δ 9.04 (s, 1H), 8.60 (d, 2H), 7.97 (m, 4H), 7.83 (s, 1H), 7.65-7.75 (m, 6H), 7.52 (m, 4H), 7.43 (m, 2H).
Example 3a.) 64.38 g (480 mmol) of 1,3-dihydro-2H-benzimidazol-2-one, 29.65 g (120 mmol) of 3-bromodibenzofurane, 27.47 g (120 mmol) of K3PO4, 6.85 g (36 mmol) of Cul and 3.41 g (24 mmol) of NN′-dimethylcyclohexanediamine were mixed together in dioxane (750 mL) at reflux under inert condition for 16 h. Dioxane was then evaporated and after work-up, the product was dissolved in CHCl3, mixed with 80 g of SiO2 and purified by chromatography (SiO2, gradient:/MeOH) to yield 17.45 g of 3-dibenzofuran-2-yl-1H-benzimidazol-2-one, 3-1 [Purity=99.8% (HPLC)] as a white powder.
Mass [M+1]=301.3
1H NMR (400 MHz, DMSO): δ 11.2 (s, 1H), 8.34 (d, 1H), 8.22 (dd, 1H), 7.88 (d, 1H), 7.76 (d, 1H), 7.64 (dd, 1H), 7.58 (m, 1H), 7.44 (m, 1H), 7.11 (m, 2H), 7.00 (m, 2H).
b.) 5.04 g (16.8 mmol) of 3-dibenzofuran-2-yl-1H-benzimidazol-2-one, 3-1, 1.63 g (8.0 mmol) of 1,3-difluoro-4,6-dinitrobenzene and 6.79 g (32 mmol) of K3PO4 were mixed together in NMP (80 mL) at 0° C. for 2h. The mixture was then stirred 2h at room temperature and precipitated in water filtrated to yield 6.43 g of 3-2 as yellow powder [Purity=90% (HPLC)] which was used directly as it is for the next step.
Mass [M+1]=765.2
c.) 6.18 g (8.0 mmol) of 3-2 and 600 mg of Pd/C 10% were mixed in 200 mL of 3:1 THF:EtOH at 50° C. under 5 bar of hydrogen for 2h. The mixture was then filtrated, the solvent is evaporated and the resulting powder was purified by chromatography (SiO2, gradient: toluene/THF) to yield 5.39 g of 3-3 [Purity=99.1% (HPLC)] as a white powder.
Mass [M+1]=705.3
d.) 3.87 g (5.5 mmol) of 3-3 and 1.77 g (9.4 mmol) of p-toluensulfonic acid were mixed together in 40 mL of methylnaphthalene at 230° C. for 12h. The dark brown mixture was cooled at 100° C., mixed with 40 g of SiO2 and purified by chromatography (SiO2, gradient: CHCl3/MeOH), recrystallized twice in acetic acid and sublimed to yield 1.47 g of 3 [Purity=99.97% (HPLC)] as a white crystal.
Mass [M+1]=669.2
1H NMR (400 MHz, TFA): 8 9.29 (s, 1H), 8.72 (d, 2H), 8.59 (d, 2H), 8.44 (s, 1H), 8.25 (d, 2H), 8.19 (d, 2H), 8.13 (m, 2H), 8.04 (m, 4H), 7.95 (m, 4H), 7.85 (m, 2H), 7.69 (m, 2H).
Example 4a.) 33.31 g (248 mmol) of 1,3-dihydro-2H-benzimidazol-2-one, 20.00 g (62.1 mmol) of 3-bromo-9-phenylcarbazol, 26.35 g (124.2 mmol) of K3PO4, 5.91 g (31.0 mmol) of Cul and 4.42 g (31.0 mmol) of NN′-dimethylcyclohexanediamine were mixed together in N,N-dimethylacetamide (350 mL) at 185° C. under inert condition for 24 h. After work-up, the product was dissolved in CHCl3, mixed with 70 g of SiO2 and purified by chromatography (SiO2, gradient: CHCl3/MeOH) to yield 15.52 g of 3-(9-phenylcarbazol-3-yl)-1H-benzimidazol-2-one, 4-1 [Purity=98% (HPLC)] as beige crystal.
Mass [M+1]=376.5
1H NMR (400 MHz, DMSO): δ 11.13 (s, 1H), 8.42 (m, 1H), 8.33 (m, 1H), 7.72 (m, 4H), 7.59 (m, 1H), 7.45-7.56 (m, 3H), 7.42 (m, 1H), 7.33 (m, 1H), 7.10 (m, 2H), 7.02 (m, 1H), 6.97 (m, 1H),
b.) 5.00 g (13.3 mmol) of 3-(9-phenylcarbazol-3-yl)-1H-benzimidazol-2-one, 4-1, 1.40 g (6.7 mmol) of 1,3-difluoro-4,6-dinitrobenzene and 5.65 g (26.6 mmol) of K3PO4 were mixed together in NMP (80 mL) at 0° C. for 2h. The mixture was then stirred 2h at room temperature and precipitated in water filtrated to yield 9.09 g of 4-2 as yellow powder [Purity=92% (HPLC)] which was used directly as it is for the next step.
Mass [M+1]=914.3
c.) 5.52 g (6.0 mmol) of 4-2 and 550 mg of Pd/C 10% were mixed in 70 mL of 3:1 THF:EtOH at 50° C. under 5 bar of hydrogen for 2h. The mixture was then filtrated, the solvent was evaporated and the resulting powder was purified by chromatography (SiO2, gradient: toluene/THF) to yield 4.6 g of 4-3 [Purity=99.0% (HPLC)] as a white powder.
Mass [M+11=854.3
d.) 3.63 g (3.6 mmol) of 4-3 and 1.17 g (2.1 mmol) of p-toluensulfonic acid were mixed together in 30 mL of methylnaphthalene at 230° C. for 12h. The dark brown mixture was cooled at 60° C. and mixed with 30 g of SiO2. It was purified by chromatography (SiO2, gradient: CHCI3/MeOH), recrystallized twice in acetic acid and sublimed to yield 0.84 g of 4 [Purity=99.81% (H PLC)] as a white crystal.
Mass [M+1]=818.2
1H NMR (400 MHz, CDCl3): δ 8.54 (d, 2H), 8.31 (s, 1H), 8.19 (m, 3H), 8.06 (d, 2H), 7.85 (dd, 2H), 7.60-7.72 (m, 10H), 7.44-58 (m, 10H), 7.31-7.42 (m, 4H).
Example 5a.)N-(2-nitrophenyl)-2-phenyl-aniline, 5-1, was prepared according to Synthesis 1980, 3, 215. 7.06 g (50.0 mmol) 1-fluoro-2-nitro-benzene and 9.31 g (55 mmol) 2-phenylaniline were stirred under nitrogen. 11.6 g (200 mmol) potassium fluoride was added. The reaction mixture was stirred at 220° C. under nitrogen for 24 h.
The reaction mixture was poured in water and was extracted with dichloromethane. The organic phase was dried with magnesium sulfate. The solvent was removed in vacuum.
Column chromatography on silica gel with hexane/toluene 15/85 gave the red product. Yield 10.3 g (71%)
1H NMR (400 MHz, CDCl3): δ 9.35 (s, 1H), 8.14 (dd, 1H), 7.32-7.48 (m, 10H), 7.18 (dd, 1H), 6.74 (td, 1H),
b.) To 10.2 g (35.0 mmol)N-(2-nitrophenyl)-2-phenyl-aniline, 5-1, in 120 ml toluene 950 mg Pd on carbon (5%) was added. The reaction mixture was stirred under 5 bar hydrogen for 3 h. The catalyst was filtered of and the solvent was removed in vacuum. Yield of 5-2: quantitative
1H NMR (400 MHz, CDCl3): δ 7.48-7.58 (m, 4H), 7.41 (tt, 1H), 7.19-7.29 (m, 2H), 7.12 (dd, 1H), 7.06 (td, 1H), 6.93 (td, 1H), 6.74-6.83 (m, 3H), 5.34 (s, 1H), 3.78 (s, 2H).
c.) 833 mg (3.20 mmol) N2-(2-phenylphenyl)benzene-1,2-diamine, 5-2, and 623 mg (3.84 mmol) di(imidazol-1-yl)methanone in 8 ml THF were stirred at 25° C. under nitrogen for 3 h.
The reaction mixture was poured in water and was extracted with dichloromethane. The organic phase was dried with magnesium sulfate. The solvent was removed in vacuum.
Column chromatography on silica gel with toluene/ethyl acetate 2/1 gave the product, 5-3. Yield 10.3 g (71%)
1H NMR (400 MHz, CDCl3): δ 9.81 (s, 1H), 7.50-7.61 (m, 4H), 7.27-7.31 (m, 2H), 7.13-7.23 (m, 3H), 6.97-7.03 (m, 2H), 6.89-6.94 (m 1H), 6.63 (d, 1H).
d.) 1-[2,4-dinitro-5-[2-oxo-3-(2-phenylphenyl)benzimidazol-1-yl]phenyl]-3-(2-phenylphenyl)benzimidazol-2-one, 5-4, was prepared according to example 1a
e.) 1-[2,4-diamino-5-[2-oxo-3-(2-phenylphenyl)benzimidazol-1-yl]phenyl]-3-(2-phenylphenyl)benzimidazol-2-one, 5-5, was prepared according to example 1b
f.) 5 was prepared according to example 1 c
a.) 1.10 g (5.00 mmol) 4-bromo-2-fluoro-1-nitro-benzene and 931 mg (5.50 mmol) 2-phenylaniline were stirred under nitrogen. 1.16 g (20.0 mmol) potassium fluoride was added. The reaction mixture was stirred at 220° C. under nitrogen for 24 h.
The reaction mixture was poured in water and was extracted with dichloromethane. The organic phase was dried with magnesium sulfate. The solvent was removed in vacuum.
Column chromatography on silica gel with hexane/toluene 15/85 gave the red product, 6-1.
1H NMR (400 MHz, CDCl3): δ 9.41 (s, 1H), 7.98 (d, 1H), 7.28-7.51 (m, 9H), 7.24 (d, 1H), 8.81 (dd, 1H).
Example 7 Example 7aTo 30.5 g (0.200 mol) 2-chlorobenzimidazole and 28.1 g (0.220 mol) 2-chloroaniline in 50 ml NMP 19.22 g (0.200 mmol) methane sulphonic acid was added. The reaction mixture was stirred at 100° C. for 18 h under nitrogen. The reaction mixture was poured on a saturated solution of sodium hydrogen carbonate in water. The water phase was extracted with ethyl acetate. The organic phase was 3 times washed with water and the organic phase was dried with magnesium sulfate. The solvent was removed in vacuum. The product was decocted in 100 ml dichloromethane.
Yield 44.8 g (92%)
1H NMR (400 MHz, DMSO-d6): δ=11.0 (s, 1H), 9.66 (s, 1H), 8.09 (t, 1H). 7.56-7.59 (m, 1H), 7.30-7.40 (m, 3H), 6.95-7.05 (m, 3H)
Example 7b25.4 g (0.100 mol) 1,4-dibromo-2-fluorobezene, 24.4 g (0.100 mol)N-(3-chlorophenyl)-1H-benzimidazol-2-amine and 63.7 g (0.300 mol) potassium phosphate tribasic in 130 ml DMA were stirred at 160° C. for 3 h under nitrogen. The reaction mixture was cooled to 25° C. The Product was filtered off and was washed with water. The product was decocted in ethanol.
Yield 34.5 g (87%).
1H NMR (400 MHz, CDCl3): δ=7.99 (d, 1H), 7.77-7.86 (m, 4H), 7.59 (t, 1H), 7.34-7.51 (m, 5H).
Example 7c19.8 g (50 mmol) 2-bromo-5-(3-chlorophenyl)benzimidazolo[1,2-a]benzimidazole, 9.00 g (50 mmol) (2-methoxycarbonylphenyl)boronic acid and 53.1 g (0.250 mol) potassium phosphate tribasic in 200 ml DMF were degassed with argon. 2.46 g (6.00 mmol) 2-Dicyclohexylphosphino-2′,6′-di-methoxybiphenyl (sPhos) and 224 mg (1.00 mmol) palladium (11) acetate were added. The reaction mixture was degassed with argon. The reaction mixture was stirred for 19 h at 100° C. under argon.
The reaction mixture was poured on water and the product was filtered off. The product was decocted with 200 ml ethanol.
Yield 15.5 g.
1H NMR (400 MHz, CDCl3): δ=7.81-7.97 (m, 6H), 7.58-7.66 (m, 3H), 7.50-7.54 (m, 2H), 7.45-7.48 (m, 1H), 7.38-7.42 (m, 1H), 7.30-7.34 (m, 2H), 3.73 (s, 3H)
Example 7dTo 0.904 g (2.00 mmol) methyl 2-[5-(3-chlorophenyl)benzimidazolo[1,2-a]benzimidazol-2-yl]benzoate in 20 ml waterfree THF, 3.13 ml (5.00 mmol) of a 1.6 M solution of methyl lithium in ether was added under argon at −78° C. The reaction mixture was warmed to 0° C. and was stirred at 0° C. for 3 h. The reaction mixture was poured on ice. A 10% solution of tartaric acid was added and the reaction mixture was extracted with dichloromethane. The organic phase was dried with magnesium sulfate. Column chromatography with toluene/ethyl acetate 10/1 gave the product.
In an alternative process, compound 7-4 was prepared as follows:
To 14.9 g (33.0 mmol) methyl 2-[5-(3-chlorophenyl)benzimidazolo[1,2-a]benzimidazol-2-yl]benzoate in 160 ml waterfree THF, 55 ml (0.165 mol) of a 3 M solution of methyl magnesium-chloride in THF was added under argon at 0° C. The reaction mixture was stirred at 50° C. for 3 h. The reaction mixture was poured on ice. A 10% solution of tartaric acid was added and the reaction mixture was extracted with dichloromethane. The organic phase was dried with magnesium sulfate. Column chromatography with toluene/ethyl acetate 10/1 gave the product.
1H NMR (400 MHz, CDCl3): δ=7.94 (t, 1H), 7.86-7.89 (m, 1H), 7.72-7.82 (m, 4H), 7.60 (t, 2H), 7.20-7.48 (m, 8h), 1.57 (s, 6H).
Example 7eTo 30.0 g PPA (polyphosphoric acid) and 22.5 g methane sulfonic acid 4.30 g (9.53 mmol) 2-[2-[5-(3-chlorophenyl)benzimidazolo[1,2-a]benzimidazol-2-yl]phenyl]propan-2-ol in in 60 ml dichloromethane was added at 0° C. The reaction mixture was stirred at 25° C. for 2 h.
The reaction mixture was poured on ice, neutralized with sodium hydrogen carbonate. The water phase was extracted with dichloromethane. The organic phase was dried with magnesium sulfate.
1H NMR (400 MHz, CDCl3): δ=8.11 (s, 1H), 7.98-7.80 (m, 5H), 7.62 (t, 1H), 7.54 (s, 1H), 7.35-7.51 (m, 6h), 1.58 (s, 6H).
Example 7f0.77 mg (1.77 mmol) of the product of example 7e, 470 mg (1.86 mmol) 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-, dioxaborolane and 520 mg (5.30 mmol) potassium acetate in 20 ml waterfree toluene were degassed with argon. 254 mg (0.532 mmol) 2-dicyclohexylphosphino-2′,4′,6′-triisoproxylbiphenyl (xPhos) and 81 mg (0.089 mmol) tris (dibenzylidene-acetone) palladium(0) (Pd2(dba)3) was added. The reaction mixture was degassed with argon. The reaction mixture was stirred for 25 h at 130° C. under argon. 1 ml water and 100 mg sodium cyanide were added. The reaction mixture was stirred at 100° C. for 1 h. The reaction mixture was poured on water and was extracted with diethyl ether. The organic phase was dried with magnesium sulfate. The product was used without purification for the next reaction.
Example 7g930 mg (1.77 mmol) of the product of example 7f, 570 mg (2.12 mmol) 2-chloro-4,6-diphenyl-1,3,5-triazine and 490 mg (3.54 mmol) potassium carbonate in a mixture of 15 ml THF, 15 ml toluene and 5 ml water were degassed with argon. 102 mg (0.089 mmol) tetrakis(triphenylphosphine)palladium(0) (Pd(Ph3)4) were added. The reaction mixture was degassed with argon. The reaction mixture was stirred for 11 h at 90° C. under argon. 10 ml of a 1% solution of sodium cyanide in water was added and the reaction mixture was stirred at 100° C. for 1 h. The product was poured on ethanol and the product was filtered off.
Column chromatography on silica gel with toluene/ethyl acetate 20/1 gave the product.
1H NMR (400 MHz, CDCl3): δ=8.29-8.30 (m, 1H), 8.91-8.94 (m, 1H), 8.81-8.84 (m, 4H), 8.33-8.36 (m, 1H), 8.20 (s, 1H), 8.02-8.04 (m, 1H), 7.82-7.85 (m, 4H), 7.36-7.66 (m, 11H), 1.61 (s, 6H).
Example 8 Example 8a3.97 mg (10 mmol) 2-bromo-5-(3-chlorophenyl)benzimidazolo[1,2-a]benzimidazole (compound 7-2, example 7b), 1.64 g mg (10 mmol) (2-acetylphenyl)boronic acid and 2.76 g (20.0 mmol) potassium carbonate in a mixture of 30 THF, 30 ml toluene and 10 ml water were degassed with argon. 580 mg (0.50 mmol) tetrakis(triphenylphosphine)palladium(0) (Pd(Ph3)4) were added. The reaction mixture was degassed with argon. The reaction mixture was stirred for 6 h at 100° C. under argon.
The reaction mixture was poured on water and the organic phase was extracted with ethyl acetate. The organic phase was dried with magnesium sulfate. The solvent was removed in vacuum. The product was decocted with ethanol.
1H NMR (400 MHz, CDCl3): δ=7.93-7.92 (m, 1H), 7.81-7.87 (m, 4H), 7.31-7.68 (10H), 2.18 (s, 3H).
Example 8bTo 1.09 g (2.50 mmol) 1-[2-[5-(3-chlorophenyl)benzimidazolo[1,2-a]benzimidazol-2-yl]phenyl]ethanone in 50 ml waterfree THF 4.2 ml (12.5 mmol) of a 3 M solution of methyl magnesium chloride in THF was added under argon at 0° C. The reaction mixture was stirred under argon for 1 h.
The reaction mixture was poured on ice. ammonium chloride was added and the reaction mixture was extracted with ethyl acetate. The organic phase was dried with magnesium sulfate.
Column chromatography with toluene/ethyl acetate 10/1 gave the product.
Example 8cCompound 7-5 was prepared as described in example 7e.
Example 8d1.00 g (2.30 mmol) of the product 7-5 of example 7e, 733 mg (3.46 mmol) dibenzofuran-2-ylboronic acid and 1.96 g (9.22 mmol) potassium phosphate tribasic in 20 ml dioxane, 50 ml toluene and 20 ml water were degassed with argon. 57 mg (0.84 mmol) 2-Dicyclohexylphosphino-2′,6′-di-methoxybiphenyl (sPhos) and 5.2 mg (0.14 mmol) palladium (II) acetate were added. The reaction mixture was degassed with argon. The reaction mixture was stirred for 4 h at 90° C. under argon.
40 ml of a 1% solution of sodium cyanide in water was added and the reaction mixture was stirred at 100° C. for 1 h. The water phase was extracted with toluene and the organic phase was dried with magnesium sulfate. The product was removed in vacuum. Column chromatography on siliga gel with dichloromethane/heptane 1/1 and then dichloromethane gave the product.
1H NMR (400 MHz, CDCl3): δ=8.28 (d, 1H), 8.19-9.20 (m, 1H), 8.16 (s, 1H), 7.99-8.03 (m, 2H), 7.86-7.90 (m, 2H), 7.79-7.85 (m, 4H), 7.70 (d, 1H), 7.61-7.64 (m, 2H), 7.36-7.53 (m, 7H), 1.58 (s, 6H).
Example 9The product was prepared as described in example 8d, whereby dibenzofuran-2-ylboronic acid was replaced by
1H NMR (400 MHz, CDCl3): δ=9.08-9-09 (m, 1H), 8.80-8.86 (m, 5H), 8.23-8.24 (m, 1H), 8.16 (s, 1H), 7.81-8.02 (m, 7H), 7.73 (t, 1H), 7.57-7.66 (m, 7H), 7.35-7.48 (m, 5H), 1.54 (s, 6H).
Example 10 Example 10aTo 38.1 g (0.250 mol) 2-chlorobenzimidazole, 25.6 g 0.275 mol) aniline in 250 ml NMP 26.4 g (0.275 mmol) methane sulphonic acid were added. The reaction mixture was stirred at 100° C. for 3 h under nitrogen. The reaction mixture was poured on a saturated solution of sodium hydrogen carbonate in water. The water phase was extracted with ethyl acetate. The organic phase was 3 times washed with water and the organic phase was dried with magnesium sulfate. The solvent was removed in vacuum. The product was decocted in 100 ml dichloromethane.
Yield 43.6 g (83%)
1H NMR (400 MHz, DMSO-d6): δ=10.9 (s, 1H), 9.38 (s, 1H), 7.29-7.36 (d, 2H), 2.29-7.36 (m, 4H), 6.96-7.02 (m, 2H), 6.91-6.94 (m, 1H).
Example 10b28.5 g (0.112 mol) 1,3-dibromo-4-fluorobezene, 23.5 g (0.112 mol)N-phenyl-1H-benzimidazol-2-amine and 59.6 g (0.281 mol) potassium phosphate tribasic in 250 ml DMA were stirred at 160° C. for 20 h under nitrogen. The reaction mixture was poured on water. The product was filtered off washed with water and ethanol.
Yield 38.9 g (97.6%).
1H NMR (400 MHz, CDCl3): δ=7.78-7.83 (m, 4H), 7.64-7.70 (m, 4H), 7.48-7.52 (m, 2H), 7.40 (dt, 1H), 7.33 (dt, 1H).
Example 10c10.9 g (30.0 mmol) of 3-bromo-5-phenyl-benzimidazolo[1,2-a]benzimidazole, 5.74 g (45.0 mmol) 2-chloroaniline and 5.77 g (60.0 mmol) potassium t-butoxide in 90 ml toluene were degassed with argon. 550 mg (0.600 mmol) Tris(dibenzylideneacetone)dipalladium(0) and 520 mg (0.900 mmol) 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (Xanphos) were added. The reaction mixture was degassed with argon. The reaction mixture was stirred for 3 h at 90° C. under argon.
The reaction mixture was poured on water and the organic phase was extracted with dichloromethane. The organic phase was dried with magnesium sulfate. The product was filtered on silica gel and was decocted with ethanol.
1H NMR (400 MHz, CDCl3): δ=7.76, 7.85 (m, 5H), 7.63 (t, 1H), 7.46 (t, 1H), 7.29-7.40 (m, 4H), 7.1-7.23 (m, 3H), 6.81-6.85 (m, 1H), 6.21 (s, 1H)
Example 10d11.1 g (27.1 mmol)N-(2-chlorophenyl)-5-phenyl-benzimidazolo[1,2-a]benzimidazol-3-amine and 11.3 g (81.4 mmol) potassium carbonate in 80 ml waterfree DMA were degassed with argon. 305 mg (1.36 mmol) palladium (II) acetate and 1.00 g (2.72 mmol) tricyclohexylphosphine tetra-fluoroborate was added. The reaction mixture was degassed with argon. The reaction was stirred at 100° C. for 19 h.
100 ml 0.5% sodium cyanide solution was added and the reaction mixture was refluxed for 2 h. The product was filtered off and washed with water and ethanol. Column chromatography on silica gel with dichloromethane/ethyl acetate 95/5 gave the product. 5.70 g (56%)
1H NMR (400 MHz, CDCl3): δ=8.41 (s, 1H), 8.32 (s, 1H), 8.21 (d, 1H), 7.98-8.02 (m, 1H), 7.89-7.92 (m, 2H), 7.80-7.84 (m, 1H), 7.62, 7.67 (m, 2H), 7.52 (s, 1H), 7.44-7.49 (m, 3H), 7.32-7.42 (m, 3H).
Example 10eTo 3.00 g (8.06 mmol) of the product 10-4 of example 10d in 60 ml waterfree THF 3.87 ml (9.67 mmol)N-butyl lithium 2.5 M in hexane were added at −78° C. under argon. The reaction was stirred at −78° C. for 1 h and 2.37 g (8.86 mmol) 2-chloro-4,6-diphenyl-1,3,5-triazine in 20 ml waterfree THF were added. The reaction mixture was stirred at −78° C. for 2 h and was then refluxed for 26 h.
The product was filtered off and was washed with ethanol, water and again with ethanol. The product was decocted in ethanol. Yield 1.18 g (24%)
1H NMR (400 MHz, TFA-d1): δ=9.68 (s, 1H), 9.35 (d, 1H), 8.97 (s, 1H), 8.60 (sb, 2H), 8.43-8.47 (m, 2H), 8.22 (sb, 2H), 7.62-7.82 (m, 16H).
Example 11To 2.59 g (6.71 mmol) of the product 10-4 of example 10d, 2.48 g (6.38 mmol) 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine 4.27 g (20.1 mmol) potassium phosphate and 510 mg (2.69 mmol) copper(I)iodide were added in 100 ml dioxane. It was stirred under nitrogen at 100° C. 7.67 g (67.3 mmol) cis,trans diaminocyclohexane was added, and the reaction mixture was stirred for 15 h. The reaction temperature was increased to 120° C., and the reaction mixture was stirred for 3.5 days.
The reaction mixture was poured on methanol and the product was filtered off. The product was washed with ethanol, water and again with ethanol. Yield 3.15 g (69%).
1H NMR (400 MHz, CDCl3): δ=9.05 (s, 1H), 8.88-8.93 (m, 1H), 7.78 (d, 4H), 8.53 (s, 1H), 8.32 (d, 1H), 8.04-8.09 (m, 1H), 7.81-7.86 (m, 5H), 7.39-7.65 (m, 14H), 7.32-7.30 (m, (under CDCl3)).
1H NMR (400 MHz, THF-d8): δ=8.18 (t, 1H), 8.98 (dt, 1H), 8.83-8.86 (m, 5H), 8.38-8.41 (m, 1H), 8.19-8.21 (m, 1H), 7.98-8.01 (m, 3H), 7.93 (t, 1H), 7.78 (s, 1H), 7.55-7.70 (m, 8H), 7.31-7.48 (m, 6H), 7.26 (dt, 1H).
Example 12 Example 12aCompound 12-3 was prepared in analogy to compound 10-3 (example 1 Oc), whereby 3-bromo-5-phenyl-benzimidazolo[1,2-a]benzimidazole was replaced by 4-bromo-5-phenyl-benzimidazolo[1,2-a]benzimidazole.
1H-NMR (400 MHz, CDCl3): δ=7.86-7.88 (m, 1H), 7.75-7.78 (m, 1H), 7.66 (dd, 1H), 7.27-7.51 (m, 9H), 7.18 (dd, 1H), 7.06 (dt, 1H), 6.95 (dd, 1H), 6.75 (dt, 1H), 5.66 (sb, 1H).
Example 12bCompound 12-4 was prepared in analogy to compound 10-4 (example 10d).
1H-NMR (400 MHz, CDCl3): δ=8.13-8.17 (m, 2H), 7.97, 7.99 (m, 1H), 7.90-7.93 (m, 2H), 7.81-7.84 (m, 2H), 7.74-7.79 (m, 2H), 7.73 (sb, 1H), 7.60-7.65 (m, 1H), 7.31-7.47 (m, 5H).
APPLICATION EXAMPLES Application Example 1A glass substrate with 120 nm-thick indium-tin-oxide (ITO) transparent electrode (manufactured by Geomatec Co., Ltd.) used as an anode was first cleaned with isopropanol in an ultrasonic bath for 10 min. To eliminate any possible organic residues, the substrate was exposed to an ultraviolet light and ozone for further 30 min. This treatment also improves the hole injection properties of the ITO. The cleaned substrate was mounted on a substrate holder and loaded into a vacuum chamber. Thereafter, the organic materials specified below were applied by vapor deposition to the ITO substrate at a rate of approx. 0.2-1 Å/sec at about 10−6-10−8 mbar. As a hole injection layer, 40 nm-thick of compound A was applied. Then 20 nm-thick of compound B was applied as a hole transporting layer. Subsequently, a mixture of 20% by weight of an emitter compound, (Ir(Ph-ppy)3), 40% by weight of a 1st host (compound C) and 40% by weight of a 2nd host (compound 2) were applied to form a 40 nm-thick phosphorescent-emitting layer. On the emitting layer, 30 nm-thick compound D was applied as an electron transport layer. Finally, 1 nm-thick LiF was deposited as an electron injection layer and 80 nm-thick Al was then deposited as a cathode to complete the device. The device was sealed with a glass lid and a getter in an inert nitrogen atmosphere with less than 1 ppm of water and oxygen.
Application Example 1 was repeated except that the host (compound 2) was replaced by compound 1. The device results are shown in Table 1.
To characterize the OLED, electroluminescence spectra were recorded at various currents and voltages. In addition, the current-voltage characteristic was measured in combination with the luminance to determine luminous efficiency and external quantum efficiency (EQE). Driving voltage U, EQE and Commission Internationale de I'Éclairage (CIE) coordinate are given at 10 mA/cm2 except otherwise stated.
The results shown in Table 1 demonstrate that the compound 2 and 1 can be used as host material in an OLED together with a green emitter.
Also, compounds 3, 4 and 5 can be used as host material in an OLED with the same structure as mentioned in application example 1 together with a green emitter. Said OLED emits green light.
Comparative Application Example 1A glass substrate with 120 nm-thick indium-tin-oxide (ITO) transparent electrode (manufactured by Geomatec Co., Ltd.) used as an anode was first cleaned with isopropanol in an ultrasonic bath for 10 min. To eliminate any possible organic residues, the substrate was exposed to an ultraviolet light and ozone for further 30 min. This treatment also improves the hole injection properties of the ITO. The cleaned substrate was mounted on a substrate holder and loaded into a vacuum chamber. Thereafter, the organic materials specified below were applied by vapor deposition to the ITO substrate at a rate of approx. 0.2-1 Å/sec at about 10−6-10−8 mbar. As a hole injection layer, 5 nm-thick of compound A′ was applied. Then 100 nm-thick of compound B′ and 60 nm-thick compound C′ were applied as hole transporting layer 1 and hole transporting layer 2, respectively. Subsequently, a mixture of 5% by weight of an emitter compound (Ir(ppy)3), 47.5% by weight of a host (comparative compound 1) and 47.5% by weight of compound E were applied to form a 40 nm-thick phosphorescent-emitting layer. On the emitting layer, 30 nm-thick compound D was applied as an electron transport layer. Finally, 1 nm-thick LiF was deposited as an electron injection layer and 80 nm-thick Al was then deposited as a cathode to complete the device. The device was sealed with a glass lid and a getter in an inert nitrogen atmosphere with less than 1 ppm of water and oxygen.
To characterize the OLED, electroluminescence spectra were recorded at various currents and voltages. In addition, the current-voltage characteristic was measured in combination with the luminance to determine luminous efficiency and external quantum efficiency (EQE). Driving voltage U and EQE are given at a current density of 10 mA/cm2, and 80% lifetime (LT80), the time spent until the initial luminance at 50 mA/cm2 was reduced to 80%, was recorded. The device results are shown in Table 2.
Comparative Application Example 2Comparative Application Example 1 was repeated except that the host (comparative compound 1) was replaced by comparative compound 2. The device results are shown in Table 2.
Comparative Application Example 1 was repeated except that the host (comparative compound 1) was replaced by compound 11. The device results are shown in Table 2.
Comparative Application Example 1 was repeated except that the host (comparative compound 1) was replaced by compound 10. The device results are shown in Table 2.
The results shown in Table 2 demonstrate that the lifetime and voltage are improved in the case that inventive compounds 11 and 10 are used as green hosts together with a co-host compound E in an OLED.
Comparative Application Example 3Comparative Application Example 1 was repeated except that the host (comparative compound 1) was replaced by comparative compound 3. The device results are shown in Table 3.
Comparative Application Example 1 was repeated except that the host (comparative compound 1) was replaced by compound 3. The device results are shown in Table 3.
The results shown in Table 3 demonstrate that the lifetime and voltage are improved in the case that an inventive compound 3 is used as a green host together with a co-host Compound E in an OLED.
Claims
1: A compound of formula (I):
- wherein:
- at least two of the substituents R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, or R7 and R8 form together one of the following ring systems:
- X is NR19, O, S, C(R28)2, or Si(R28)2;
- R9 and R19 are independently of each other group of formula -(A1)o-(A2)p(A3)q-(A4)r-R20;
- R1, R2, R3, R4, R5, R6, R7, R8, which are not forming together a ring system of formula IIa, IIb or IIc are independently of each other H, CN or group of formula -(A1′)o′-(A2′)p′-(A3′)q′-(A4′)r′-R20′ or a group E,
- or adjacent groups R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, and/or R7 and R8 can from together a ring;
- R10, R11, R12, R13 are independently of each other H, CN or group of formula -(A1′)o′-(A2′)p′-(A3′)q′-(A4′)r′-R20′ or a group E, or
- adjacent groups R10 and R11, R11 and R12 and/or R12 and R13 can from together a ring;
- o is 0, or 1, p is 0, or 1, q is 0, or 1, r is 0;
- o′ is 0, or 1, p′ is 0, or 1, q′ is 0, or 1, r′ is 0, or 1,
- A1, A2, A3, A4 are independently of each other a C6-C24 arylene group which is unsubstituted or substituted by G, C2-C24 heteroarylene group which is unsubstituted or substituted by G;
- R20 is a C6-C30 aryl group which is unsubstituted or substituted by G, C2-C60 heteroaryl group which is unsubstituted or substituted by G, a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D,
- or, in the case that at last one of o, p, q and r is 1, R20 is CN;
- A1′, A2′, A3′, A4′ are independently of each other a C6-C24 arylene group which is unsubstituted or substituted by G, C2-C24 heteroarylene group which is unsubstituted or substituted by G;
- R20′ is H, CN, a C6-C30 aryl group which is unsubstituted or substituted by G, C2-C60 heteroaryl group which is unsubstituted or substituted by G, a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D;
- R28 is independently of each other C6-C18aryl which is unsubstituted or substituted by C1-C18alkyl or C1-C18alkoxy; or C1-C18alkyl which is interrupted by —O—, which is unsubstituted or substituted by E,
- or two residues R28 can together with the carbon atom or Si atom to which they are bonded form a ring;
- D is —CO—, —COO—, —S—, —SO—, —SO2—, —O—, -CR63═CR64—, —NR65—, —SiR70R71—, —POR72—, or —C≡C;
- E is —OR69, —SR69, —NR65R66, —COR68, —COOR67, —CONR65R66, —CN, —Si(R70)3 or halogen;
- G is E, or a C1-C24alkyl group, a C6-C24aryl group, a C6-C24aryl group, which is substituted by F, C1-C24alkyl, C1-C24alkyl which is interrupted by O, a C2-C30heteroaryl group, or a C2-C30heteroaryl group, which is substituted by F, C1-C24alkyl, C1-C24alkyl which is interrupted by O;
- R63 and R64 are independently of each other C6-C18aryl; C6-C18aryl which is substituted by C1-C18alkyl or C1-C18alkoxy; C1-C18alkyl; or C1-C18alkyl which is interrupted by —O—;
- R65 and R66 are independently of each other a C6-C18aryl group; a C6-C18aryl which is substituted by C1-C18alkyl or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—, or
- R65 and R66 together form a five or six membered ring;
- R67 is a C6-C18aryl group; a C6-C18aryl group, which is substituted by C1-C18alkyl, or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—;
- R68 is H; a C6-C18aryl group; a C6-C18aryl group, which is substituted by C1-C18alkyl or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—;
- R69 is a C6-C18aryl; a C6-C18aryl, which is substituted by C1-C18alkyl or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—;
- R70 and R71 are independently of each other a C1-C18alkyl group, a C6-C18aryl group, or a C6-C18aryl group, which is substituted by C1-C18alkyl; and
- R72 is a C1-C18alkyl group, a C6-C18aryl group, or a C6-C18aryl group, which is substituted by C1-C18alkyl;
- wherein the dotted lines are bonding sites.
2: The compound of formula (I) as claimed in claim 1, wherein X is NR19 or C(R28)2.
3: The compound of formula (I) as claimed in claim 1, wherein two of the substituents R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, or R7 and R8 form together a ring system of formula IIa, IIb or IIc.
4: The compound of formula (I) as claimed in claim 1, wherein:
- at least two of the substituents R1 and R2, R2 and R3, R3 and R4, or R6 and R7form together a ring system of formula IIa, IIb or IIc, preferably a ring system of formula IIa or IIb; or
- at least two of the substituents R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, or R7 and R8 form together a ring system of formula (IIc).
5: The compound of formula (I) as claimed in claim 4, having the formula (I-IIb), (I-IIb′), (I′-II′c), (I′-II′c′), (I-IIc), (I-IIc′), (I′-II′ca), (I′-II′c′a), (I-IIca), (I-IIc′a), (I″-IIcb), (I-IIc″b), (I″-II″cb), (I″-II″c″b), (I′″-IIcb), (I-IIc′″b), (I′″-II′″cb), (I′″-II′″c′″b), (I″-IIca), (I-IIc″a), (I″-II″c″a), (I-IIc′″a), (I′″-II′″ca) or (I′″-II′″c′″a:
- wherein R1 and R4 and R5 and R8.
6: The compound of formula (I) as claimed in claim 1, wherein R1, R2, R3, R4, R5, R6, R7 and R8, which are not forming together a ring system of formula IIa, IIb or IIc are H, or one of R5, R6, R7 and R8 is CN and/or a C6-C18 aryl group which is unsubstituted or substituted G, a C2-C18 heteroaryl group which is unsubstituted or substituted G, a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D, and all other R1, R2, R3, R4, R5, R6, R7 and R8 are H; or R1, R2, R3, R4, R5, R6, R7 and R8, which are not forming together a ring system of formula IIa, IIb or IIc are independently of each other H, CN or one of R1, R2, R3 and R4 is a C6-C18 aryl group which is unsubstituted or substituted G, a C2-C18 heteroaryl group which is unsubstituted or substituted G or a C1-C25alkyl group, which can optionally be substituted by E and/or interrupted by D, and all other R1, R2, R3, R4, R5, R6, R7 and R8 are H.
7: The compound of formula (I) as claimed in claim 1, wherein R10, R1, R12 and R13 are H, or one of R10, R11, R12 and R13 is CN and/or a C6-C18 aryl group which is unsubstituted or substituted G, a C2-C18 heteroaryl group which is unsubstituted or substituted G, a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D, and all other R10, R1, R12 and R13 are H.
8: The compound of formula (I) as claimed in claim 1, wherein A1, A2, A3, A4, A1′, A2′, A3′ and A4′ are independently of each other a group of the following formula:
- which can be unsubstituted or substituted by G whereby G is defined above;
- R73 is a C6-C18aryl group; a C6-C18aryl which is substituted by C1-C18alkyl or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O;
- R38 a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G, or a C1-C24heteroaryl group, which can optionally be substituted by G; and/or two adjacent groups of the groups may form together with the atom to which they are bonded a ring structure, which can optionally be substituted by G;
- R130 is independently in each occurrence H or C6-C24arylene group, which can optionally be substituted by G, or a C2-C30heteroarylene group, which can optionally be substituted by G; wherein G is as defined in above; wherein the dotted lines are bonding sites;
- wherein (C)— has the meaning that the bonding site of the group A1, A2, A3, A4, A1′, A2′, A3′ and A4′ is linked to a C-atom, and (N)— has the meaning that the bonding site of the group A1, A2, A3, A4, A1′, A2′, A3′ and A4′ is linked to a N-atom, and (C,N) has the meaning that the bonding site of the group A1, A2, A3, A4, A1′, A2′, A3′ and A4′ is linked to a C or N-atom.
9: The compound of formula (I) as claimed in claim 1, wherein R20′ is H, CN or a group of the following formula and R20 is independently of R20′ a group of the following formula: or, in the case that at last one of o, p, q and r is 1, CN;
- wherein:
- X1 is S, O, C(R21)2, NR23;
- R22 is a C6-C18 aryl group which is unsubstituted or substituted by G, C2-C18 heteroaryl group which is unsubstituted or substituted by G;
- R23 is H, a C6-C18 aryl group which is unsubstituted or substituted by G, C2-C18 heteroaryl group which is unsubstituted or substituted by G;
- R24 and R25 are independently of each other H, a C6-C18 aryl group which is unsubstituted or substituted by G, C2-C18 heteroaryl group which is unsubstituted or substituted by G, a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D, or —CN;
- a is 0, 1, 2 or 3;
- b is 0, 1, 2, 3 or 4;
- the dotted lines are bonding sites; or
- wherein:
- X1, X2 and X3 are independently of each other CR16 or N, wherein in formula (8) at least one of X1 to X3 is N, and wherein in formulae (9) and (10) at least one of X1 and X3 is N;
- Ar1 and Ar2 are independently of each other a C6-C24 aryl group, which is optionally substituted by G, or a C1-C24 heteroaryl group, which is optionally substituted by G;
- R16, R17 and R18 are independently of each other H, a C6-C24 aryl group which can be substituted by G, a C1-C24 heteroaryl group which can be substituted by G or a C1-C25alkyl group, which can optionally be substituted by E and/or interrupted by D; or
- R26, R27, R28 and R29 are independently of each other H, a C6-C24 aryl group which can be substituted by G, a C1-C24 heteroaryl group which can be substituted by G or a C1-C25alkyl group, which can optionally be substituted by E and/or interrupted by D; or a substituent E;
- e is 0, 1, 2, 3, 4 or 5;
- f is 0, 1, 2 or 3;
- g is 0, 1, 2, 3 or 4;
- h is 0, 1 or 2;
- or
- two adjacent groups R26, R27 R28 or R29 may form together with the atoms to which they are bonded a ring structure which may be substituted by G,
- wherein ˜ is a bonding site.
10: An organic electronic device, comprising the compound according to claim 1.
11: The organic electronic device according to claim 10, which is an organic electroluminescent device, wherein the organic electroluminescent device comprises an organic thin film layer between a cathode and an anode, wherein the organic thin film layer comprises one or more layers and comprises a light emitting layer, and at least one layer of the organic thin film layer comprises the compound of formula (I).
12: The organic electronic device according to claim 11, wherein the light emitting layer comprises the compound of formula (I).
13: The organic electronic device according to claim 11, wherein the light emitting layer comprises a phosphorescent material, which is an ortho-metallated complex comprising a metal atom selected from the group consisting of iridium (Ir), osmium (Os) and platinum (Pt).
14: A charge transport layer, charge/exciton blocking layer, or an emitting layer comprising the compound according to claim 1.
15: The emitting layer according to claim 14, comprising the compound of formula (I) as host material in combination with a phosphorescent emitter.
16: An apparatus selected from the group consisting of stationary visual display units; mobile visual display units; illumination units; keyboards;
- items of clothing; furniture; wallpaper, the apparatus comprising the organic electronic device according to claim 10.
17: A device, comprising the compound of claim 1, wherein the device is selected from the group consisting of organic electroluminescent devices, electrophotographic photoreceptors, photoelectric converters, organic solar cells, switching elements, organic light emitting field effect transistors, image sensors and dye lasers.
18: A process for preparing the compound of claim 1, the process comprising:
- i) preparing the compound of formula (I), wherein R6 and R7 form together a ring system of formula IIa, comprising: ia) preparing an intermediate of formula IIIa;
- and ib) cyclizing the intermediate to form the compound of formula (I);
- ii) preparing the compound of formula (I), wherein R2 and R3 form together a ring system of formula IIb, comprising: iia) preparing an intermediate of formula IIIb or IIIb′:
- and iib) cyclizing the intermediate to form the compound of formula (I);
- iii) preparing the compound of formula (I), wherein R2 and R3 form together a ring system of formula IIc, comprising: iiia) preparing an intermediate of formula IIIc:
- and iiib) cyclizing the intermediate to form the compound of formula (IIId):
- and iiic) functionalizing the NH group to form the compound of formula (I);
- iv) preparing the compound of formula (I), wherein R2 and R3 form together a ring system of formula IIc, comprising: iva) preparing an intermediate of formula IIIe:
- and ivb) cyclizing the intermediate to form the compound of formula (I);
- v) preparing the compound of formula (I), wherein R6 and R7 form together a ring system of formula IIc, comprising: va) preparing an intermediate of formula (IIIf):
- and vb) cyclizing the intermediate to form the compound of formula (I);
- vi) preparing the compound of formula (I), wherein R6 and R7 form together a ring system of formula IIc, comprising: via) preparing an intermediate of formula (IIIg):
- and vib) cyclizing the intermediate to form the compound of formula (I);
- vii) preparing the compound of formula (I), wherein R6 and R7 form together a ring system of formula IIc, comprising: viia) preparing an intermediate of formula (IIIh):
- and viib) cyclizing the intermediate to form the compound of formula (I);
- viii) preparing the compound of formula (I), wherein R6 and R7 form together a ring system of formula IIc, comprising: viiia) preparing an intermediate of formula (IIIi):
- wherein Hal is halogen; viiib) cyclizing the intermediate to form a compound of formula (IIIj):
- and viiic) functionalizing the NH group to form the compound of formula (I);
- ix) preparing the compound of formula (I), wherein R2 and R3 form together a ring system of formula IIc, comprising: ixa) preparing an intermediate of formula (IIIk):
- wherein Hal is halogen; ixb) cyclizing the intermediate to form a compound of formula (IIIl):
- ixc) functionalizing the NH group to form the compound of formula (I);
- wherein:
- R9 is a group of formula -(A1)o-(A2)p-(A3)q(A4)r-R20;
- R1, R2, R3, R4, R5, R6, R7, R8, which are not forming together a ring system of formula IIa, IIb or IIc are independently of each other H, CN or group of formula -(A1′)o′-(A2′)p′-(A3′)q′-(A4′)r′-R20′ or a group E,
- or adjacent groups R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, and/or R7 and R8 can from together a ring;
- R10, R11, R12, R13 are independently of each other H, CN or group of formula -(A1′)o′-(A2′)p′-(A3′)q′-(A4′)r′-R20′ or a group E, or
- adjacent groups R10 and R11, R11 and R12 and/or R12 and R13 can from together a ring;
- o is 0, or 1, p is 0, or 1, q is 0, or 1, r is 0, or 1;
- o′ is 0, or 1, p′ is 0, or 1, q′ is 0, or 1, r′ is 0, or 1,
- A1, A2, A3, A4 is a C6-C24 arylene group which is unsubstituted or substituted by G, C2-C24 heteroarylene group which is unsubstituted or substituted by G;
- R20 is a C6-C24 aryl group which is unsubstituted or substituted by G, C2-C18 heteroaryl group which is unsubstituted or substituted by G, a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D; or, in the case that at last one of o, p, q and r is 1, R20 is CN;
- A1′, A2′, A3′, A4′ is a C6-C24 arylene group which is unsubstituted or substituted by G, C2-C24 heteroarylene group which is unsubstituted or substituted by G;
- R20′ is H, CN or a C6-C24 aryl group which is unsubstituted or substituted by G, C2-C18 heteroaryl group which is unsubstituted or substituted by G, a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D;
- R25 is independently of each other C6-C18aryl which is unsubstituted or substituted by C1-C18alkyl or C1-C51alkoxy; or C1-C18alkyl which is interrupted by —O—, which is unsubstituted or substituted by E;
- D is —CO—, —COO—, —S—, —SO—, —SO2—, —O—, -CR63═CR64—, —NR65—, —SiR70R71—, —POR72—, or —C≡C;
- E is —OR69, —SR69, —NR65R66, —COR68, —COOR67, —CONR65R66, —CN, —Si(R70)3 or halogen;
- G is E, or a C1-C24alkyl group, a C6-C24aryl group, a C6-C24aryl group, which is substituted by F, C1-C24alkyl, C1-C24alkyl which is interrupted by O, a C2-C30heteroaryl group, or a C2-C30heteroaryl group, which is substituted by F, C1-C24alkyl, C1-C24alkyl which is interrupted by O;
- R63 and R64 are independently of each other C6-C18aryl; C6-C18aryl which is substituted by C1-C18alkyl or C1-C18alkoxy; C1-C18alkyl; or C1-C18alkyl which is interrupted by —O—;
- R65 and R66 are independently of each other a C6-C18aryl group; a C6-C18aryl which is substituted by C1-C18alkyl or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C51alkyl group, which is interrupted by —O—, or
- R65 and R66 together form a five or six membered ring,
- R67 is a C6-C18aryl group; a C6-C18aryl group, which is substituted by C1-C18alkyl, or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—;
- R68 is H; a C6-C18aryl group; a C6-C18aryl group, which is substituted by C1-C18alkyl or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—;
- R69 is a C6-C18aryl; a C6-C18aryl, which is substituted by C1-C18alkyl or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—;
- R70 and R71 are independently of each other a C1-C18alkyl group, a C6-C18aryl group, or a C6-C18aryl group, which is substituted by C1-C18alkyl; and
- R72 is a C1-C18alkyl group, a C6-C18aryl group, or a C6-C18aryl group, which is substituted by C1-C18alkyl.
19: A compound represented by any one of the following of formulae:
- wherein:
- R9 is a group of formula -(A1)o-(A2)p-(A3)q (A4)r-R20;
- R1, R2, R3, R4, R5, R6, R7, R8, which are not forming together a ring system of formula IIa, IIb or IIc are independently of each other H, CN or group of formula -(A1′)o′-(A2′)p′-(A3′)q′-(A4)r′-R20′ or a group E, or
- adjacent groups R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, and/or R7 and R8 can from together a ring;
- R10, R11, R12, R13 are independently of each other H, CN or group of formula -(A1′)o′-(A2′)p′-(A3′)q′-(A4′)r′-R20′ or a group E; or CN;
- adjacent groups R10 and R11, R11 and R12 and/or R12 and R13 can from together a ring;
- o is 0, or 1, p is 0, or 1, q is 0, or 1, r is 0, or 1;
- o′ is 0, or 1, p′ is 0, or 1, q′ is 0, or 1, r′ is 0, or 1,
- A1, A2, A3, A4 is a C6-C24 arylene group which is unsubstituted or substituted by G, C2-C24 heteroarylene group which is unsubstituted or substituted by G;
- R20 is a C6-C24 aryl group which is unsubstituted or substituted by G, C2-C18 heteroaryl group which is unsubstituted or substituted by G, a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D; or, in the case that at last one of o, p, q and r is 1, R20 is CN;
- A1′, A2′, A3′, A4′ is a C6-C24 arylene group which is unsubstituted or substituted by G, C6-C24 heteroarylene group which is unsubstituted or substituted by G;
- R20′ is H, CN, or a C6-C24 aryl group which is unsubstituted or substituted by G, C2-C18 heteroaryl group which is unsubstituted or substituted by G, a C1-C25alkyl group, which can optionally be substituted by E and or interrupted by D;
- R28 is independently of each other C6-C18aryl which is unsubstituted or substituted by C1-C18alkyl or C1-C18alkoxy; or C1-C51alkyl which is interrupted by —O—, which is unsubstituted or substituted by E;
- D is —CO—, —COO—, —S—, —SO—, —SO2—, —O—, -CR63═CR64—, —NR65—, —SiR70R71—, —POR72—, or —C≡C;
- E is —OR69, —SR69, —NR65R66, —COR68, —COOR67, —CONR65R66, —CN, —Si(R70)3 or halogen;
- G is E, or a C1-C24alkyl group, a C6-C24aryl group, a C6-C24aryl group, which is substituted by F, C1-C24alkyl, C1-C24alkyl which is interrupted by O, a C2-C30heteroaryl group, or a C2-C30heteroaryl group, which is substituted by F, C1-C24alkyl, C1-C24alkyl which is interrupted by O;
- R63 and R64 are independently of each other C6-C18aryl; C6-C18aryl which is substituted by C1-C18alkyl or C1-C18alkoxy; C1-C18alkyl; or C1-C18alkyl which is interrupted by —O—;
- R65 and R66 are independently of each other a C6-C18aryl group; a C6-C18aryl which is substituted by C1-C18alkyl or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—, or
- R65 and R66 together form a five or six membered ring,
- R67 is a C6-C18aryl group; a C6-C18aryl group, which is substituted by C1-C18alkyl, or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—;
- R68 is H; a C6-C18aryl group; a C6-C18aryl group, which is substituted by C1-C18alkyl or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—;
- R69 is a C6-C18aryl; a C6-C18aryl, which is substituted by C1-C18alkyl or C1-C18alkoxy; a C1-C18alkyl group; or a C1-C18alkyl group, which is interrupted by —O—;
- R70 and R71 are independently of each other a C1-C18alkyl group, a C6-C18aryl group, or a C6-C18aryl group, which is substituted by C1-C18alkyl; and
- R72 is a C1-C18alkyl group, a C6-C18aryl group, or a C6-C18aryl group, which is substituted by C1-C18alkyl.
Type: Application
Filed: Dec 2, 2016
Publication Date: Jan 3, 2019
Patent Grant number: 11174258
Applicant: Idemitsu Kosan Co., Ltd. (Chiyoda-ku, Tokyo)
Inventors: Thomas SCHAFER (Liestal), Jean-Charles FLORES (Rixheim), Hideaki NAGASHIMA (Basel)
Application Number: 15/780,688
